CN107405891A - Cosmetic sheet - Google Patents

Cosmetic sheet Download PDF

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Publication number
CN107405891A
CN107405891A CN201680018573.4A CN201680018573A CN107405891A CN 107405891 A CN107405891 A CN 107405891A CN 201680018573 A CN201680018573 A CN 201680018573A CN 107405891 A CN107405891 A CN 107405891A
Authority
CN
China
Prior art keywords
layer
resin
cosmetic sheet
superficial layer
superficial
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201680018573.4A
Other languages
Chinese (zh)
Inventor
须藤昌利
名木义幸
片冈咲惠
鹰野阳子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to CN202110398898.2A priority Critical patent/CN113147109A/en
Publication of CN107405891A publication Critical patent/CN107405891A/en
Pending legal-status Critical Current

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Classifications

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/24—Pressing or stamping ornamental designs on surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
    • B44C3/02—Superimposing layers
    • B44C3/025—Superimposing layers to produce ornamental relief structures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31931—Polyene monomer-containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention provides a kind of cosmetic sheet that the excellent design sense brought by concaveconvex shape and hand sense of touch can be assigned to synthetic resin.At least lamination has substrate layer, formed by the solidfied material of hardening resin composition and has the superficial layer of concaveconvex shape and the thermoplastic resin film layer that can be peeled off the cosmetic sheet successively.

Description

Cosmetic sheet
Technical field
The present invention relates to the cosmetic sheet that can assign the excellent design sense brought by concaveconvex shape and hand sense of touch.
Background technology
Vehicle interior part, building materials built-in material, household electrical appliances framework etc. use the surface stack in synthetic resin to have dress The decorated resin products formed of spike.Also, in recent years, with the variation of consumer demand, demand is various to be possessed and sets The decorated resin products formed of meter property.In order to follow so diversified consumer demand, it is expected that developing surface has bumps Shape, not only there is design sense, hand sense of touch also good decorated resin products formed.
In the prior art, when manufacturing decorated resin products formed, make to impart design in advance using by injection moulding Property the cosmetic sheet forming method integrated with resin, in decorated resin products formed of the manufacture formed with concaveconvex shape, use Surface has the cosmetic sheet of concaveconvex shape.
But in the case where using the cosmetic sheet manufacture decorated resin products formed with concaveconvex shape, by cosmetic sheet When being provided in injection moulding or preforming (vacuum forming) before this, Yin Re or pressure cause concaveconvex shape to deform or disappear Lose, therefore the cosmetic sheet after injection moulding is unable to maintain that initial concaveconvex shape, existing fully to assign by concaveconvex shape The shortcomings that design sense brought and hand sense of touch.
In order to overcome the shortcomings that such, it was recently reported that following method：Formed by being embossed processing on thermoplastic matrix piece The surface of concavo-convex cosmetic sheet, the cushion that is made up of extrusion molding or hot melt application method lamination thermoplastic resin, from And suppress the deformation or disappearance of concaveconvex shape caused by vacuum forming or injection moulding, the cushion is removed after injection moulding Go (referring for example to patent document 1).
But in method disclosed in patent document 1, the buffering that is set to suppress the deformation of concaveconvex shape or disappearance Layer is formed by the extrusion molding or hot melt application method of thermoplastic resin, thus the micro concavo-convex on thermoplastic matrix piece surface be present The problem of shape easily deforms or disappeared because of the heat of the thermoplastic resin of melting.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-137216 publications
The content of the invention
Invention technical problems to be solved
It is a primary object of the present invention to：There is provided that synthetic resin can be assigned and excellent set by what concaveconvex shape was brought Meter sense and the cosmetic sheet of hand sense of touch.The present invention also aims to：There is provided using the cosmetic sheet decorated resin products formed and Their manufacture method.
For solving the means of technical problem
In order to solve the above-mentioned technical problem, the present inventor has made intensive studies.As a result find at least to fold successively Layer has substrate layer, formed by the solidfied material of hardening resin composition and has the superficial layer of concaveconvex shape and can peel off The cosmetic sheet of thermoplastic resin film layer, by the thermoplastic resin film layer that can be peeled off, can effectively it protect by curability tree The concaveconvex shape for the superficial layer that the solidfied material of oil/fat composition is formed.Also, by using the cosmetic sheet, vacuum forming can be suppressed Or the change or disappearance of the concaveconvex shape occurred during injection moulding, decorated resin products formed can be assigned and be brought by concaveconvex shape Excellent design sense and hand sense of touch.The first invention of the present invention is to be based on the opinion, and research is further repeated and completes 's.
That is, the first invention provides the invention of following manner.
A kind of 1. cosmetic sheets of item, at least lamination has substrate layer, formed by the solidfied material of hardening resin composition successively for it And there is the superficial layer of concaveconvex shape and the thermoplastic resin film layer that can be peeled off.
2. cosmetic sheet as described in item 1, above-mentioned superficial layer by ionizing radiation curable resin combination solidfied material shape Into.
3. cosmetic sheet as described in item 1 or 2 of item, above-mentioned thermoplastic resin film layer contain non-crystalline polyester resin.
4. cosmetic sheet as any one of item 1~3 of item, above-mentioned thermoplastic resin film layer pass through extrusion molding or thermosphere Pressure is stacked on the concaveconvex shape of above-mentioned superficial layer.
5. cosmetic sheet as any one of item 1~4, above-mentioned thermoplastic resin film layer is by the bumps of above-mentioned superficial layer The recess landfill of shape.
6. cosmetic sheet as any one of item 1~5 of item, between above-mentioned superficial layer and above-mentioned thermoplastic resin film layer Lamination has bonding adhesive linkage.
7. cosmetic sheet as any one of item 1~6 of item, has priming coat in the lower stacks close to above-mentioned superficial layer.
8. cosmetic sheet as any one of item 1~7 of item, lamination has figure between above-mentioned substrate layer and above-mentioned superficial layer Pattern layer.
9. cosmetic sheet as any one of item 1~8 of item, the concaveconvex shape of above-mentioned superficial layer are convex by what is partly set Portion and the recess of lower floor of above-mentioned superficial layer is exposed between raised part formed.
10. cosmetic sheet as any one of item 1~9 of item, the thickness of above-mentioned superficial layer is 0.01~30 μm.
A kind of 11. manufacture methods of cosmetic sheet of item, it includes：
The first process of laminated body is formed, the laminated body has with concaveconvex shape and by curability tree in substrate layer superimposed layer The superficial layer that the solidfied material of oil/fat composition is formed；With
On the above-mentioned superficial layer of the laminated body obtained in above-mentioned first process, thermoplastic resin film that lamination can be peeled off Second process of layer.
The manufacture method of 12. cosmetic sheet as described in item 11 of item, above-mentioned thermoplastic resin film layer contain amorphism polyester Resin.
The manufacture method of 13. cosmetic sheet as described in item 11 or 12 of item, above-mentioned second process include following process：
On superficial layer, by extrusion molding or heat lamination, the recess of the concaveconvex shape of above-mentioned superficial layer is filled The process of above-mentioned thermoplastic resin film layer that can peel off of mode lamination.
The manufacture method of 14. cosmetic sheet as described in item 11 or 12 of item, above-mentioned second process include following process：
The coating resin composition on superficial layer, folded in a manner of the recess of the concaveconvex shape of above-mentioned superficial layer is filled The process of layer bonding adhesive linkage；With
The process that the above-mentioned thermoplastic resin film layer that can be peeled off is formed on above-mentioned bonding adhesive linkage.
A kind of 15. decorated resin products formeds with thermoplastic resin film layer of item, at least lamination has moulding resin successively for it Layer, substrate layer, formed by the solidfied material of hardening resin composition and there is the superficial layer of concaveconvex shape and the heat that can be peeled off Plastic resin film layer.
A kind of 16. manufacture methods of the decorated resin products formed with thermoplastic resin film layer of item, it is included in item 1~10 Any one of cosmetic sheet substrate layer side by injecting resin and the process of laminated forming resin bed.
A kind of 17. manufacture methods of decorated resin products formed of item, it includes carrying thermoplastic resin film from described in item 15 The process that the decorated resin products formed of layer peels off above-mentioned thermoplastic resin film layer.
In addition, the present inventor in order to solve the above-mentioned technical problem carried out deeper into research.As a result find：Extremely Few lamination successively has superficial layer with concaveconvex shape and the concavo-convex protective layer that can peel off and concavo-convex protective layer are from superficial layer The cosmetic sheet for possessing the adhesive linkage of the recess landfill of the concaveconvex shape of superficial layer and peeling off film layer successively is played in side, passes through bumps Protective layer can effectively protect the concaveconvex shape of superficial layer.Also, by using the cosmetic sheet, can suppress vacuum forming or The deformation or disappearance of the concaveconvex shape occurred during injection moulding, it can assign what is brought by concaveconvex shape to decorated resin products formed Excellent design sense and hand sense of touch.The second invention of the present invention is to be based on the opinion, and research is further repeated and completes.
That is, the second invention provides the invention of following manner.
A kind of 18. cosmetic sheets, its concavo-convex protection that at least lamination has superficial layer with concaveconvex shape and can peeled off Layer,
Above-mentioned concavo-convex protective layer possesses successively from above-mentioned photons fills out the recess of the concaveconvex shape of above-mentioned superficial layer The adhesive linkage and stripping film layer buried.
19. cosmetic sheet as described in item 18 of item, above-mentioned adhesive linkage are formed by the solidfied material of curable resin.
20. cosmetic sheet as described in item 18 or 19 of item, above-mentioned concavo-convex protective layer possesses de- successively from above-mentioned photons Mold layer, above-mentioned adhesive linkage and above-mentioned stripping film layer,
Above-mentioned release layer and above-mentioned adhesive linkage fill the recess of the concaveconvex shape of above-mentioned superficial layer.
21. cosmetic sheet as any one of item 18~20 of item, above-mentioned release layer is by ionizing radiation curable resin group The solidfied material of compound is formed.
22. cosmetic sheet as any one of item 18~21 of item, above-mentioned superficial layer consolidating by hardening resin composition Compound or resin film are formed.
23. cosmetic sheet as any one of item 18~22 of item, has primary coat in the lower stacks close to above-mentioned superficial layer Layer.
24. cosmetic sheet as any one of item 18~23 of item, in above-mentioned superficial layer and above-mentioned concavo-convex protective layer phase Anti- side lamination has patterned layer.
A kind of 25. manufacture methods of cosmetic sheet of item, including：
Prepare the first process of the superficial layer with concaveconvex shape；
On above-mentioned superficial layer, the coating adhesive in a manner of the recess of the concaveconvex shape of above-mentioned superficial layer to be filled, Second process of lamination adhesive linkage；With
In the 3rd process of the superimposed layer stripping film layer of above-mentioned adhesive linkage.
The manufacture method of 26. cosmetic sheet as described in item 25 of item, above-mentioned first process include following process：
Lamination patterned layer and the process of priming coat successively on substrate layer；
Processing is embossed on above-mentioned priming coat, in the process that the surface of above-mentioned priming coat forms concaveconvex shape；With
Hardening resin composition is coated with above-mentioned priming coat, makes its solidification afterwards, lamination has concaveconvex shape The process of superficial layer.
The manufacture method of 27. cosmetic sheet as described in item 25 of item, above-mentioned first process include following process：
Prepare the process of superficial layer being made up of resin film；With
Processing is embossed on above-mentioned superficial layer, in the process that the surface of above-mentioned superficial layer forms concaveconvex shape.
The manufacture method of 28. cosmetic sheet as described in item 25 of item, above-mentioned first process include following process：
Lamination patterned layer and the process of priming coat successively on above-mentioned substrate layer；
The laminated resin film on above-mentioned priming coat, the process of stack surface layer；With
Processing is embossed on above-mentioned superficial layer, in the process that the surface of above-mentioned superficial layer forms concaveconvex shape.
A kind of 29. decorated resin products formeds with concavo-convex protective layer of item, at least lamination has forming resin layer, tool successively for it There are the superficial layer of concaveconvex shape and the concavo-convex protective layer that can be peeled off,
Above-mentioned concavo-convex protective layer possesses successively from above-mentioned photons fills out the recess of the concaveconvex shape of above-mentioned superficial layer The adhesive linkage and stripping film layer buried.
A kind of 30. manufacture methods of decorated resin products formed, it is included from the concavo-convex protective layer that carries described in item 29 The process that decorated resin products formed peels off concavo-convex protective layer.
A kind of 31. manufacture methods of the decorated resin products formed with concavo-convex protective layer of item, it is included in item 18~24 The process that the photons of cosmetic sheet described in any one form forming resin layer by injecting resin.
Invention effect
In accordance with the invention it is possible to provide synthetic resin can be assigned the excellent design sense that be brought by concaveconvex shape and The cosmetic sheet of hand sense of touch.Also, in accordance with the present invention it is further possible to provide using the decorated resin products formed of the cosmetic sheet and they Manufacture method.
Brief description of the drawings
Fig. 1 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 2 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 3 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 4 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 5 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 6 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 7 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the first invention.
Fig. 8 is the cross section structure of a mode of the decorated resin products formed with thermoplastic resin film layer of the first invention Schematic diagram.
Fig. 9 is the cross section structure of a mode of the decorated resin products formed with thermoplastic resin film layer of the first invention Schematic diagram.
Figure 10 is the schematic diagram of the cross section structure of a mode of the decorated resin products formed of the first invention.
Figure 11 is the schematic diagram of the cross section structure of a mode of the decorated resin products formed of the first invention.
Figure 12 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the second invention.
Figure 13 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the second invention.
Figure 14 is the schematic diagram of the cross section structure of a mode of the cosmetic sheet of the second invention.
Figure 15 is the cross section structure of a mode of the decorated resin products formed with concavo-convex protective layer of the second invention Schematic diagram.
Figure 16 is the schematic diagram of the cross section structure of a mode of the decorated resin products formed of the second invention.
Embodiment
1. cosmetic sheet
The cosmetic sheet of first invention is characterised by that at least lamination has substrate layer, by hardening resin composition successively Solidfied material forms and has the superficial layer of concaveconvex shape and the thermoplastic resin film layer that can be peeled off.
In addition, the cosmetic sheet of the second invention is characterised by, at least lamination has superficial layer with concaveconvex shape and can The concavo-convex protective layer of stripping, above-mentioned concavo-convex protective layer possess the concaveconvex shape of above-mentioned superficial layer successively from above-mentioned photons Recess landfill adhesive linkage and peel off film layer.
Wherein, in this manual, unless otherwise specified, " (methyl) acrylic acid " means " acrylic acid or methyl-prop Olefin(e) acid ", other similar statements and same implication.In addition, the cosmetic sheet of the present invention can not possess patterned layer etc., such as Can be transparent.
The cosmetic sheet of the present invention is described in detail below.Wherein, in following record, in the first invention and Different contents can clearly state in two inventions, be identical in case of no particular description, thus in the second invention Omit and record.For example, in the first invention and the second invention, substrate layer 1, ionizing radiation curable resin, release layer 32, primary coat Layer 4, patterned layer 5, shielding layer, transparent resin layer 6, each composition of back side adhesive linkage are identicals.In addition, on being protected with bumps The manufacture method of the decorated resin products formed of sheath, except using the second invention cosmetic sheet instead of the first invention cosmetic sheet with Outside, it is identical.
The laminated construction of cosmetic sheet
The cosmetic sheet of first invention is with least lamination has substrate layer 1, the solidfied material by hardening resin composition successively Formed and there is the superficial layer 2 of concaveconvex shape and the laminated construction for the thermoplastic resin film layer 30 that can be peeled off.Superficial layer 2 can To be made up of multilayer.
In the first invention superficial layer 2 and thermoplastic resin film layer 30 can direct lamination, can also be between, the layers Other layers of lamination.In the case of direct multilayer thermoplastic resin film layer 30, thermoplastic resin film layer 30 turns into protection superficial layer 2 Concaveconvex shape concavo-convex protective layer 3.In addition, lamination has the feelings of other layers between superficial layer 2 and thermoplastic resin film layer 30 Under condition, other layers and thermoplastic resin film layer 30 can play a role as concavo-convex protective layer 3.As other layers, such as can To enumerate bonding adhesive linkage 31, release layer 32 etc..
In the first invention, in the case where lamination has other layers, from the side of superficial layer 2, lamination has bonding adhesive linkage 31/ The laminated body of thermoplastic resin film layer 30, lamination have the laminated body of the thermoplastic resin film layer 30 of release layer 32/, lamination to have release layer The laminated body of the 32/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/ is able to play a role as concavo-convex protective layer 3.
In the first invention, release layer 32 fills the recess of the concaveconvex shape of superficial layer 2.In bonding adhesive linkage 31 by gluing Dosage form is connect in the case of, bonding adhesive linkage 31 fills the recess of the concaveconvex shape of superficial layer 2.In addition, in lamination release layer 32 and the bonding adhesive linkage 31 that is formed by bonding agent in the case of, in the cosmetic sheet of the first invention, release layer 32 and bonding are viscous Layer 31 is connect to fill the recess of the concaveconvex shape of superficial layer 2.Wherein, as described later, bonding adhesive linkage 31 refers to adhesive linkage or viscous Layer is closed, is formed by bonding agent or adhesive.
In the cosmetic sheet of the first invention, between substrate layer 1 and superficial layer 2, in order to improve each mutual cementability of layer, Priming coat 4 can be arranged as required to.In the case where forming superficial layer 2 by multilayer, for example, can by multiple-level surface layer 2 across The lamination of priming coat 4.
In addition, in the first invention, between substrate layer 1 and superficial layer 2 or substrate layer 1 one opposite with superficial layer 2 Side, in order to assign dicoration, patterned layer 5 can be arranged as required to.In the case where setting priming coat 4, at substrate layer 1 and bottom Patterned layer 5 is set between coating 4.Patterned layer 5 can set multilayer.
In addition, in the first invention, between substrate layer 1 and superficial layer 2, in order to suppress the change of the color of substrate layer 1 Or it is irregular, shielding layer (not shown) can be arranged as required to.In the case where setting priming coat 4, the shielding layer is arranged on base Between material layer 1 and priming coat 4, in addition, in the case where setting patterned layer 5, the shielding layer is arranged on substrate layer 1 and pattern Between layer 5.
Also,, can be according to need in order to improve marresistance between substrate layer 1 and superficial layer 2 in the first invention Transparent resin layer 6 is set.In the case where setting priming coat 4, the transparent resin layer 6 be arranged on patterned layer 5 and priming coat 4 it Between.
Also, in the cosmetic sheet of the first invention, in order to improve decorated resin products formed shaping when and moulding resin it is close Conjunction property, in the back side of substrate layer 1 (face of the side opposite with superficial layer 2) back side adhesive linkage can be set (not scheme as needed Show).
In the cosmetic sheet of the first invention, in order to improve the marresistance of decorated resin products formed, weatherability etc., Ke Yi Close to the lower section (side opposite with thermoplastic resin film layer 30) of superficial layer 2, resin bed 7 is set.The feelings of resin bed 7 are being set , can be as needed close under resin bed 7 in order to improve resin bed 7 and adaptation of layer for being disposed below etc. under condition Side (side opposite with superficial layer 2) sets bond layer (not shown).
As the example of the laminated construction of the cosmetic sheet of the first invention, can enumerate：Lamination has the surface of substrate layer 1/ successively The laminated construction of 2/ thermoplastic resin film layer 30 of layer；Lamination has the superficial layer 2/ of substrate layer 1/ to bond the thermoplasticity of adhesive linkage 31/ successively The laminated construction of resin film layer 30；Lamination has the release layer 32/ of 1/ superficial layer of substrate layer 2/ to bond the thermoplastic resin of adhesive linkage 31/ successively The laminated construction of adipose membrane layer 30；Lamination has the lamination knot of the thermoplastic resin film layer 30 of 1/ patterned layer of substrate layer, 5/ superficial layer 2/ successively Structure；Lamination has the laminated construction of the superficial layer 2/ of 1/ patterned layer of the substrate layer 5/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/ successively； Lamination has the folded of the release layer 32/ of 1/ patterned layer of substrate layer, the 5/ superficial layer 2/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/ successively Rotating fields；Lamination has the laminated construction of the thermoplastic resin film layer 30 of 4/ superficial layer of substrate layer 1/ patterned layer, 5/ priming coat 2/ successively； Lamination has the lamination of the superficial layer 2/ of 1/ patterned layer of substrate layer, the 5/ priming coat 4/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/ successively Structure；Lamination has the release layer 32/ of 4/ superficial layer of substrate layer 1/ patterned layer, 5/ priming coat 2/ to bond the thermoplastic resin of adhesive linkage 31/ successively The laminated construction of adipose membrane layer 30；Lamination has the thermoplastic of 4/ superficial layer of substrate layer 1/ patterned layer, 5/ transparent resin layer, 6/ priming coat 2/ successively The laminated construction of property resin film layer 30；Lamination has the superficial layer 2/ of 6/ priming coat of substrate layer 1/ patterned layer, 5/ transparent resin layer 4/ successively Bond the laminated construction of the thermoplastic resin film layer 30 of adhesive linkage 31/；Lamination has the transparent resin layer of 1/ patterned layer of substrate layer 5/ successively The release layer 32/ of 6/ priming coat, 4/ superficial layer 2/ bonds the laminated construction of the thermoplastic resin film layer 30 of adhesive linkage 31/；Lamination has successively 1/ patterned layer of substrate layer 5/, 6/ bond layer of the transparent resin layer/heat of the release layer 32/ of 7/ superficial layer of resin bed 2/ bonding adhesive linkage 31/ The laminated construction of plastic resin film layer 30；Lamination has the priming coat of 5/ transparent resin layer of patterned layer 5/ substrate layer, 1/ patterned layer 6/ successively The release layer 32/ of 4/ superficial layer 2/ bonds the laminated construction of the thermoplastic resin film layer 30 of adhesive linkage 31/；Lamination has substrate layer 1/ successively The release layer 32/ of 4/ superficial layer of patterned layer 5/ transparent resin layer, 6/ superficial layer, 2/ priming coat 2/ bonds the thermoplastic resin of adhesive linkage 31/ The laminated construction of film layer 30；Lamination has the superficial layer of 4/ resin bed of substrate layer 1/ patterned layer, 5/ transparent resin layer, 6/ priming coat 7/ successively Laminated construction of the 2/ release layer 32/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/ etc..
In Fig. 1~Fig. 3, as a mode of the laminated construction of the cosmetic sheet of the first invention, represent that lamination has successively The sectional view of the cosmetic sheet of the thermoplastic resin film layer 30 of 1/ superficial layer of substrate layer 2/.In Fig. 4, the cosmetic sheet as the first invention Laminated construction a mode, represent successively lamination have the superficial layer of 6/ priming coat of substrate layer 1/ patterned layer, 5/ transparent resin layer 4/ The sectional view of the cosmetic sheet of the 2/ release layer 32/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/.In Figure 5, as the first invention Cosmetic sheet one mode of laminated construction, represent successively lamination have the priming coat 4/ of 1/ patterned layer of substrate layer, 5/ transparent resin layer 6/ The sectional view of the cosmetic sheet of the release layer 32/ of 7/ superficial layer of the resin bed 2/ bonding thermoplastic resin film layer 30 of adhesive linkage 31/.In Fig. 6 In, as a mode of the laminated construction of the cosmetic sheet of the first invention, represent that lamination has the figure of 5/ substrate layer of patterned layer 1/ successively The release layer 32/ of 4/ superficial layer of pattern layer 5/ transparent resin layer, 6/ priming coat 2/ bonds the dress of the thermoplastic resin film layer 30 of adhesive linkage 31/ The sectional view of spike.In the figure 7, as the first invention cosmetic sheet laminated construction a mode, represent successively lamination have The heat of the release layer 32/ of 4/ superficial layer of substrate layer 1/ patterned layer, 5/ transparent resin layer, 6/ superficial layer, 2/ priming coat 2/ bonding adhesive linkage 31/ The sectional view of the cosmetic sheet of plastic resin film layer 30.
The bumps that the cosmetic sheet of second invention has superficial layer 2 with concaveconvex shape with least lamination and can peeled off The laminated construction of protective layer 3.
Concavo-convex protective layer 3 possesses the adhesive linkage of the recess landfill of the concaveconvex shape of superficial layer 2 successively from the side of superficial layer 2 34 and peel off film layer 33., can also in concavo-convex protective layer 3 in order to improve fissility of superficial layer 2 and concavo-convex protective layer 3 etc. Lamination has release layer 32, adhesive linkage 34 and peels off film layer 33 successively from the side of superficial layer 2.Wherein, have in concavo-convex protective layer 3 de- In the case of mold layer 32, in the cosmetic sheet of the second invention, release layer 32 and adhesive linkage 34 are by the recessed of the concaveconvex shape of superficial layer 2 Portion fills.
In the cosmetic sheet of the second invention, in the side opposite with concavo-convex protective layer 3 of superficial layer 2, base material can be set 1 supporting mass as cosmetic sheet of layer etc..
In the cosmetic sheet of the second invention, in the side opposite with concavo-convex protective layer 3 of superficial layer 2, in order to improve each layer Mutual cementability, priming coat 4 can be arranged as required to.
In addition, in the side opposite with concavo-convex protective layer 3 of superficial layer 2, in order to assign dicoration, can set as needed Placing graphic pattern layer 5.In the case where setting substrate layer 1 and priming coat 4, setting patterned layer 5 is between substrate layer 1 and priming coat 4 Can.
In addition, in the case where setting substrate layer 1, between substrate layer 1 and superficial layer 2, in order to suppress the face of substrate layer 1 The change of color is irregular, can be arranged as required to shielding layer (not shown).In the case where setting priming coat 4, the shielding layer It is arranged between substrate layer 1 and priming coat 4, in addition, in the case where setting patterned layer 5, the shielding layer is arranged on base material Between layer 1 and patterned layer 5.
Also,, can be as needed in order to improve marresistance in the side opposite with concavo-convex protective layer 3 of superficial layer 2 Transparent resin layer 6 is set.In the case where setting priming coat 4, the transparent resin layer 6 is arranged between patterned layer 5 and priming coat 4 .
Also, in the cosmetic sheet of the second invention, in order to improve when decorated resin products formed is molded and moulding resin Adaptation, back side adhesive linkage can be set (not on the surface of the side opposite with concavo-convex protective layer 3 of superficial layer 2 as needed Diagram).
As the example of the laminated construction of the cosmetic sheet of the second invention, can enumerate：Lamination has superficial layer 2/ concavo-convex successively The laminated construction of protective layer 3 (adhesive linkage 34/ peels off film layer 33)；Lamination has 1/ superficial layer of substrate layer, 2/ concavo-convex protective layer 3 successively The laminated construction of (adhesive linkage 34/ peels off film layer 33)；Lamination has 1/ patterned layer of substrate layer, 5/ superficial layer, 2/ concavo-convex protective layer 3 successively The laminated construction of (adhesive linkage 34/ peels off film layer 33)；Lamination has 1/ patterned layer of substrate layer, 5/ priming coat, 4/ superficial layer 2/ recessed successively The laminated construction of convex protective layer 3 (adhesive linkage 34/ peels off film layer 33)；Lamination has the table of 1/ patterned layer of substrate layer, 5/ priming coat 4/ successively The laminated construction of the concavo-convex protective layer 3 of surface layer 2/ (adhesive linkage 34/ of release layer 32/ peels off film layer 33)；Lamination has substrate layer 1/ successively 5/ transparent resin layer of patterned layer, 6/ priming coat, 4/ superficial layer, 2/ concavo-convex protective layer 3 (adhesive linkage 34/ of release layer 32/ peels off film layer 33) The laminated construction laminated construction that lamination forms successively etc..In Figure 12 and Figure 13, the lamination as the cosmetic sheet of the second invention One mode of structure, represent that lamination has 1/ superficial layer of substrate layer, 2/ concavo-convex protective layer 3 successively (adhesive linkage 34/ peels off film layer 33) Cosmetic sheet sectional view.In fig. 12, as the second invention cosmetic sheet laminated construction a mode, expression fold successively Layer has 6/ priming coat of substrate layer 1/ patterned layer, 5/ transparent resin layer, 4/ superficial layer, the 2/ concavo-convex (adhesive linkage of release layer 32/ of protective layer 3 33/ peels off film layer 33) the laminated construction cosmetic sheet that lamination forms successively sectional view.
The composition of each layer of cosmetic sheet
[substrate layer 1]
Substrate layer 1 is the resin for the effect that supporting mass is played in the cosmetic sheet of (the first invention and the second invention) of the invention Piece (resin film).On resin component used in substrate layer 1, it is not particularly limited, is set according to three-dimensionally shaped property and with shaping Compatibility of fat etc. suitably selects, and preferably enumerates the resin film being made up of thermoplastic resin.As the thermoplastic resin, tool Body can enumerate acrylonitrile-butadiene-styrene resin (being also denoted as sometimes below " ABS resin "), acrylonitrile-benzene second The polyolefin trees such as alkene-acrylate (being also denoted as sometimes below " ASA resin "), acrylic resin, polypropylene, polyethylene Fat, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) etc..Among these, from three-dimensionally shaped property From the viewpoint of preferably ABS resin and acrylic resin.In addition, substrate layer 1 can be formed by the single-layer sheet of these resins, may be used also With by of the same race or not homogenous resins multilayer chips into.
On the modulus of elasticity in static bending of substrate layer 1, it is not particularly limited.For example, make the present invention using insert-molding method Cosmetic sheet it is integrated with moulding resin in the case of, the elasticity of flexure of the substrate layer 1 at 25 DEG C in cosmetic sheet of the invention Modulus can enumerate 500~4,000MPa, preferably enumerate 750~3,000MPa.Here, modulus of elasticity in static bending at 25 DEG C is base In the value that JIS K7171 are measured.For modulus of elasticity in static bending at 25 DEG C in more than 500MPa, cosmetic sheet possesses sufficient rigidity, Even if for insert-molding method, surface characteristic and mouldability also become more preferable.In addition, modulus of elasticity in static bending at 25 DEG C is 3, During below 000MPa, when being manufactured in a manner of roll-to-roll, enough tension force can be applied, be not likely to produce relaxation, figure can not be made Printing, so-called pattern good apposition is repeated to case displacement.
, can be as needed to its one or two sides in order to improve the adaptation of the layer with setting thereon on substrate layer 1 Implement the surface treatment physically or chemically of oxidizing process, further provided for contouring method etc..The oxidation carried out as the surface treatment of substrate layer 1 Method, it can enumerate such as Corona discharge Treatment, chromium oxidation processes, flame treatment, hot blast processing, ozone-ultraviolet line facture. In addition, the further provided for contouring method carried out as the surface treatment of substrate layer 1, can be enumerated such as sand-blast, solvent treatment method.This A little surface treatments can suitably select according to the species for the resin component for forming substrate layer 1, from the viewpoint of effect and operability etc. Set out, preferably enumerate Corona discharge Treatment method.
Also, substrate layer 1 can also implement the known processing for forming adhesive linkage etc..
, can also be without coloring also, substrate layer 1 can be coloured using colouring agent.In addition, substrate layer 1 can be with It is water white transparency, tinted clear and translucent any form.As colouring agent used in substrate layer 1, it is not particularly limited, It is preferred that enumerating colouring agent also non-discolouring under the temperature conditionss more than 150 DEG C, known dry colour, paste can be specifically enumerated Pigment, master batch resin composition etc..
The thickness of substrate layer 1 can according to the appropriate setting such as the purposes of cosmetic sheet, method of forming integrated with moulding resin, 25~1000 μm or so, 50~700 μm or so can generally be enumerated.More specifically, supplied by the cosmetic sheet of the present invention When insert-molding method, as the thickness of substrate layer 1, can generally enumerate 50~1000 μm or so, be preferably 100~700 μm, More preferably 100~500 μm.In addition, when by the cosmetic sheet of the present invention for injection moulding decorative method simultaneously, as substrate layer 1 thickness, it can generally enumerate 25~200 μm, be preferably 50~200 μm, more preferably 70~200 μm.
[superficial layer 2]
In the first invention, superficial layer 2 has concaveconvex shape, (contains curable resin by hardening resin composition Resin combination) solidfied material formed.So, by being formed by the solidfied material of hardening resin composition with concaveconvex shape Superficial layer 2, when can suppress thermoplastic resin film layer 30 described later being stacked on the superficial layer 2 concaveconvex shape deform or Disappear.Therefore, by using the cosmetic sheet of the first invention, with using in the thermoplastic matrix as the superficial layer with concaveconvex shape The situation of the existing cosmetic sheet for the thermoplastic resin film layer that body piece superimposed layer can be peeled off is compared, and can obtain having excellent Design sense and the decorated resin products formed of hand sense of touch.Superficial layer 2 can be made up of multilayer.The feelings of superficial layer 2 are being made up of multilayer , can be by multiple-level surface layer 2 across the lamination of priming coat 4 under condition, such as shown in Fig. 7., can be right by forming superficial layer by multilayer Each superficial layer assigns different functions.
In addition, in the second invention, superficial layer 2 has concaveconvex shape, preferably by the solidfied material of hardening resin composition Or resin film is formed.
＜ concaveconvex shapes ＞
In the first invention and the second invention, the concaveconvex shape that is formed on superficial layer 2 is not particularly limited, according to Design sense and the hand sense of touch for wishing to assign etc. is appropriate to be set.As the concaveconvex shape, such as hairline decorative pattern, wood can be enumerated Line decorative pattern, geometry decorative pattern (point-like, strip, carbon fiber shape) etc..
In addition, the height of convex portion, the width of convex portion, adjacent convex portion in the concaveconvex shape formed on superficial layer 2 Between spacing, the width etc. of recess, according to the appropriate setting such as design sense and hand sense of touch for wishing to assign.
For example, the center line average roughness (Ra) as superficial layer 2, excellent set by what concaveconvex shape was brought from assigning From the viewpoint of meter sense and hand sense of touch, 1.0~20 μm, more preferably preferably 1.0~10 μm, 1.5~5 μ can be generally enumerated m., will not be because of bumps when cosmetic sheet is rolled into tubular keeping etc. when the center line average roughness of superficial layer 2 is below 20 μm It is excessively obvious and cause to occur during transport scratch or rupture, reel it is loose etc., be preferable.
In addition, from the same viewpoint, as maximum height (Rmax), 1.0~100 μm can be generally enumerated, preferably For 1.0~80 μm, more preferably 1.0~60 μm.From the same viewpoint, generally can be with as 10 average heights (Rz) Enumerate 1.0~100 μm, more preferably preferably 1.0~80 μm, 1.0~60 μm.Wherein, center line average roughness (Ra), most Big height (Rmax) and 10 average heights (Rz) are the values measured respectively using surface roughness-contour shape measuring machine.
In addition, in the first invention, the concaveconvex shape that is formed by superficial layer 2 can be recessed in the manner shown in figure 1 The bottom in portion is formed by superficial layer 2；Mode that can also be as shown in Figures 2 and 3 is such, and the lower floor of superficial layer 2 is at the bottom of recess Portion exposes, and superficial layer 2 is partly set, and forms convex portion.From protection decorated resin products formed surface from the viewpoint of, preferably before Person.Fig. 1 and Fig. 2 represents the concaveconvex shape for example formed by implementing the method for embossing processing described later, and Fig. 3 represents for example to pass through The resin combination for forming superficial layer 2 is only coated on to form the part (protuberance layer) of convex portion and make what its method solidified was formed Concaveconvex shape.I.e., in figure 3, the concaveconvex shape of superficial layer 2 exposes above-mentioned by the convex portion that partly sets and between raised part The recess of the lower floor of superficial layer is formed.For convenience, Fig. 1~Fig. 3 represents that lamination has substrate layer 1, superficial layer 2 and can shelled successively From thermoplastic resin film layer 30 laminated construction.
From the viewpoint of possessing excellent design sense and hand sense of touch, patterned layer 5 preferably is set and by table in cosmetic sheet The recess for the concaveconvex shape that surface layer 2 is formed reaches the patterned layer 5.
On the other hand, in the second invention, the concaveconvex shape formed by superficial layer 2 can be such in a manner of as shown in figure 12 The bottom of recess is formed by superficial layer 2, can also as shown in fig. 13 that the such superficial layer 2 of mode lower floor recess bottom reveal Go out, set multiple lobe portions of superficial layer 2.From protection decorated resin products formed surface from the viewpoint of, preferably the former. Wherein, for convenience, Figure 12 and Figure 13 represent that lamination successively has the laminated construction of substrate layer 1, superficial layer 2 and concavo-convex protective layer 3.
In the cosmetic sheet of the first invention and the second invention, in order to assign the high matter brought by concaveconvex shape to cosmetic sheet Sense, above-mentioned concaveconvex shape are at least formed in subregion.That is, in the cosmetic sheet of the present invention, above-mentioned relation is met Concaveconvex shape can be formed in subregion, can also be formed in Zone Full.
＜ forms ＞
, can as curable resin in the solidfied material of the hardening resin composition of superficial layer 2 of the first invention is formed To enumerate thermosetting resin, ionizing radiation curable resin etc., preferably ionizing radiation curable resin.By by containing ionization spoke The solidfied material for penetrating the resin combination of curable resin forms the superficial layer with concaveconvex shape, and utilizes thermoplasticity described later Resin film layer covers the superficial layer, can suppress the deformation or disappearance of concaveconvex shape occurred when vacuum forming or injection moulding, Especially excellent design sense and hand sense of touch can be assigned to decorated resin products formed.
On the other hand, the resin film as the superficial layer 2 for forming the second invention, can enumerate thermoplastic resin film.As Thermoplastic resin, it can enumerate and gather such as polyethylene terephthalate (PET), PEN (PEN) Ester resin, acrylic resin etc., preferably acrylic resin.In the case where forming superficial layer 2 by resin film, superficial layer 2 Generally there is independence, the effect as supporting mass can be played.Therefore, in this case, the cosmetic sheet of the first invention can With without substrate layer 1.
In the first invention and the second invention, as thermosetting resin, such as polyurethane resin, epoxy resin can be enumerated Deng.Thermosetting resin can be used alone, and two or more can also be applied in combination.In the situation using thermosetting resin Under, by by the thermosetting resin lamination before solidification and making it be heating and curing, superficial layer 2 can be formed.In addition, on ionization Radiation-hardenable resins are as described below.
(ionizing radiation curable resin)
In the first invention and the second invention, ionizing radiation curable resin used in formation superficial layer 2 refers to pass through The resin for irradiating ionizing ray and crosslinking, solidifying.Wherein, ionizing ray here refers to penetrate in electromagnetic wave or charged particle There is the ray that can make molecule aggregation or the quanta of energy of crosslinking, usually using ultraviolet (UV) or electron ray in line (EB), additionally including the charged particle ray such as the electromagnetic waves such as X ray, gamma-rays, alpha ray, ion irradiation.Consolidate in ionising radiation In the property changed resin, electron ray curing resin can realize solvent free, it is not necessary to photopolymerization initiator, can obtain steady Fixed curing characteristics, thus be adapted to use when forming superficial layer.
As ionizing radiation curable resin, can specifically enumerate will have polymerism unsaturated bond or epoxy radicals in molecule The resin that suitably mixes of prepolymer, oligomer and/or monomer.
As the above-mentioned oligomer as ionizing radiation curable resin, there is free-radical polymerised insatiable hunger preferably in molecule With (methyl) acrylate oligomer of group, wherein it is preferred that intramolecular has more than 2 (more than 2 functions) polymerisms unsaturations Multi-functional (methyl) acrylate oligomer of key.As multi-functional (methyl) acrylate oligomer, such as can arrange Lift makrolon (methyl) acrylate, acrylic acid silicone (methyl) acrylate, polyurethane (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, polybutadiene (methyl) acrylate, There is cationically polymerizable functional group in silicone (methyl) acrylate, silicone-modified polyurethane (methyl) acrylate, molecule Oligomer (such as phenolic resin varnish type epoxy resin, bisphenol-type epoxy resin, aliphatic ethylene base ether, aromatic ethenyl ether Deng) etc..Here, makrolon (methyl) as long as there is carbonic acid ester bond and end or side in acrylate main polymer chain Chain has (methyl) acrylate-based material, is not particularly limited, such as can be incited somebody to action by using (methyl) acrylic acid Polycarbonate polyol is esterified and obtained.Makrolon (methyl) acrylate for example can be to have gathering for polycarbonate backbone Urethane (methyl) acrylate etc..Polyurethane (methyl) acrylate with polycarbonate backbone for example can be by making poly- carbon Acid esters polyalcohol, polyhydric isocyanate compound and hydroxyl (methyl) acrylate reactions and obtain.Acrylic acid silicone (methyl) Acrylate can be free-radical polymerized and acquisition by the way that silicone-macromers and (methyl) acrylate monomer occurs.Poly- ammonia Ester (methyl) acrylate for example can will be by PPG or PEPA and polyisocyanate by using (methyl) acrylic acid The urethane oligomer that the reaction of cyanate obtains is esterified and obtained.Epoxy (methyl) acrylate for example can be by making (first Base) the epoxide ring reaction of the acrylic acid bisphenol-type epoxy resin relatively low with molecular weight or phenolic resin varnish type epoxy resin is esterified And obtain.And can also use as two alkaline carboxylic acid anhydrides by epoxy (methyl) acrylate it is partially modified obtained from carboxyl Epoxy (methyl) acrylate of modified version.Polyester (methyl) acrylate for example can will be by by using (methyl) acrylic acid Two ends of be condensed to yield of polybasic carboxylic acid and polyalcohol have the polyester oligomer of hydroxyl hydroxy esterification or by using (methyl) acrylic acid will obtain to the hydroxy esterification of the end of oligomer obtained from polybasic carboxylic acid addition oxyalkylene.Polyethers (methyl) acrylate can obtain the hydroxy esterification of PPG by using (methyl) acrylic acid.Polybutadiene (methyl) acrylate can by the side chain of polybutadiene oligomer addition (methyl) acrylic acid obtain.Silicone (first Base) acrylate can pass through on main chain with polysiloxanes key silicone end or side chain on addition (methyl) acrylic acid And obtain.Silicone-modified polyurethane (methyl) acrylate for example can be by making hydroxyl (methyl) acrylate and having silane The silicone compounds of alcohol radical react and obtained with the polyurethane prepolymer with NCO.These oligomer can individually make With a kind, two or more can also be applied in combination.
In addition, as the above-mentioned monomer as ionizing radiation curable resin, have preferably in molecule free-radical polymerised (methyl) acrylate monomer of unsaturated group, wherein it is preferred that multi-functional (methyl) acrylate monomer.As multifunctional Property (methyl) acrylate monomer, as long as intramolecular has (methyl) acrylate list of more than 2 polymerism unsaturated bonds Body.As multi-functional (methyl) acrylate monomer, ethylene glycol two (methyl) acrylate, the third two can be specifically enumerated It is alcohol two (methyl) acrylate, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, new Pentanediol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, hydroxy new pentane acid neopentyl glycol two (methyl) third Olefin(e) acid ester, bicyclopentyl two (methyl) acrylate, caprolactone modification dicyclopentenyl two (methyl) acrylate, oxirane Modified phosphate two (methyl) acrylate, allylation cyclohexyl two (methyl) acrylate, isocyanuric acid ester two (methyl) third Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, propionic acid are modified dipentaerythritol three (methyl) acrylate, (first of pentaerythrite three Base) acrylate, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acrylyl oxy-ethyl) isocyanuric acids Ester, propionic acid are modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, ethylene-oxide-modified Dipentaerythritol six (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..These monomers can To be used alone a kind, two or more can also be applied in combination.
In these ionizing radiation curable resins, touched to the more excellent design sense of decorated resin products formed imparting and hand From the viewpoint of sense, preferably enumerating in molecule has polymerism unsaturated bond or the oligomer of epoxy radicals, more preferably enumerates poly- carbon Acid esters (methyl) acrylate, acrylic acid silicone (methyl) acrylate, particularly preferably enumerate makrolon (methyl) acrylic acid Ester.
In addition, in these ionizing radiation curable resins, from the viewpoint for assigning especially excellent design sense and hand sense of touch Set out, preferably enumerate (1) makrolon (methyl) acrylate and (2) other multi-functional (methyl) acrylate (more officials Can property (methyl) acrylate oligomer or monomer) combination, more preferably enumerate (1) makrolon (methyl) acrylate with (2) combination of multi-functional polyurethane (methyl) acrylate.
Used by the ionizing radiation curable resin combination of the ionizing radiation curable resin of above-mentioned (1) and above-mentioned (2) In the case of, on their ratio, the setting such as their molecular weight, functional group number is considered, for example, the electricity of above-mentioned (1) From radiation-hardenable resins and the mass ratio (ionizing radiation curable of above-mentioned (1) of the ionizing radiation curable resin of above-mentioned (2) Shu Zhi ﹕ above-mentioned (2) ionizing radiation curable resin) ﹕ 1 or so of 50 ﹕ 50~99 preferably are enumerated, more preferably enumerate the ﹕ of 80 ﹕ 20~99 1 or so, particularly preferably enumerate the ﹕ 1 or so of 85 ﹕ 15~99.
Below, the makrolon (first to being suitable as using for forming the ionizing radiation curable resin of superficial layer 2 Base) acrylate and multi-functional polyurethane (methyl) acrylate be described in detail.
Makrolon (methyl) acrylate
Makrolon (methyl) as long as acrylate main polymer chain with carbonic acid ester bond and end or side chain with The material of (methyl) acrylate, is not particularly limited, such as can be the polyurethane (first with polycarbonate backbone Base) acrylate etc..In addition, it is somebody's turn to do in (methyl) acrylate, from the viewpoint of crosslinking, solidification is become good, as every 1 The functional group number of molecule, preferably enumerate 2~6.The preferred end of makrolon (methyl) acrylate or side chain have more than 2 Multifunctional makrolon (methyl) acrylate of (methyl) acrylate.Makrolon (methyl) acrylate can individually make With a kind, two or more can also be applied in combination.
Above-mentioned makrolon (methyl) acrylate for example can be by a part for the hydroxyl of polycarbonate polyol or complete Portion replaces with (methyl) acrylate (acrylate or methacrylate) and obtained.The esterification can be by common Esterification is carried out.It can enumerate for example：1) make polycarbonate polyol with acryloyl halide or metering system carboxylic acid halides depositing in alkali In the lower method being condensed, 2) make polycarbonate polyol and acrylic anhydride or methacrylic anhydride in the presence of a catalyst 3) method that is condensed makes polycarbonate polyol be carried out in the presence of acid catalyst with acrylic or methacrylic acid Method of condensation etc..
Above-mentioned polycarbonate polyol be main polymer chain with carbonic acid ester bond, end or side chain with more than 2, preferably The polymer of 2~50, more preferably 3~50 hydroxyls.The manufacture method of the representative of the polycarbonate polyol can enumerate by The side of polycondensation reaction occurs for diatomic alcohol compounds (A), more than 3 yuan of polyalcohol (B) and the compound (C) as carbonyl component Method.
The diatomic alcohol compounds (A) that raw material as polycarbonate polyol uses are by formula HO-R1- OH is represented. This, R1It is the divalent alkyl of carbon number 2~20, can contains ehter bond in group.For example, the alkylidene of straight chain or straight-chain, Cycloalkylidene, phenylene.
As the concrete example of above-mentioned diatomic alcohol compounds, ethylene glycol, 1,2-PD, diethylene glycol, dipropyl can be enumerated Glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 3- methyl- Double (2- hydroxyl-oxethyls) benzene of 1,5- pentanediols, 1,6-HD, 1,8- ethohexadiols, 1,3-, double (the 2- hydroxyls of 1,4- Ethyoxyl) benzene, neopentyl glycol, 1,4- cyclohexanediols, 1,4 cyclohexane dimethanol etc..These dihydric alcohols can be used alone 1 Kind, two or more can also be applied in combination.
In addition, the example of more than 3 yuan of the polyalcohol (B) as the raw material as polycarbonate polyol, can be enumerated Trimethylolpropane, trimethylolethane, pentaerythrite, two-trimethylolpropane, dipentaerythritol, glycerine, D-sorbite etc. Alcohols.In addition, more than 3 yuan of the polyalcohol can be the epoxy with the equivalent of hydroxyl addition 1~5 relative to above-mentioned polyalcohol The alcohols of ethane, expoxy propane or hydroxyl obtained from other epoxyalkane.These polyalcohols can be used alone, Two or more can be applied in combination.
Compound (C) as the carbonyl component of the raw material as polycarbonate polyol is selected from carbonic diester, phosphinylidyne Arbitrary compound in chlorine or their equivalents.As the compound, dimethyl carbonate, carbonic acid two can be specifically enumerated The carbonic diester class such as ethyl ester, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate；Phosgene；Chloro-carbonic acid Halogen formate esters such as methyl esters, ethyl chloroformate, phenyl chloroformate etc..These compounds can be used alone, and can also incite somebody to action Two or more is applied in combination.
Polycarbonate polyol can be by making above-mentioned diatomic alcohol compounds (A), more than 3 yuan of polyalcohol (B) and being used as The compound (C) of carbonyl component occurs polycondensation reaction under conditions of common and synthesized.Diatomic alcohol compounds (A) and polyalcohol (B) addition molar ratio is such as set in the range of the ﹕ 1 of 50 ﹕ 50~99.In addition, on the chemical combination as carbonyl component Thing (C) relative to diatomic alcohol compounds (A) and polyalcohol (B) addition mol ratio, for example, it can be set to relative to dihydric alcohol Hydroxyl possessed by compound and polyalcohol is in the range of 0.2~2 equivalent.
As with the equivalent of the hydroxyl in the presence of the polycarbonate polyol after the generation polycondensation reaction of above-mentioned additional proportion Number (eq./mol), the average out to more than 3 for example in 1 molecule can be enumerated, be preferably 3~50, more preferably 3~20.Meeting , can be acrylate-based by (methyl) of esterification described later formation necessary amount during such equivalents, and can be right Makrolon (methyl) acrylate assigns the flexibility of appropriateness.Wherein, the functional end-group of the polycarbonate polyol leads to Often it is OH bases, but one part can be carbonate group.
The manufacture method of polycarbonate polyol described above is for example documented in Japanese Unexamined Patent Application 64-1726 publications In.In addition, the polycarbonate polyol can also pass through poly- carbon as described in Japanese Unexamined Patent Publication 3-181517 publications The ester exchange reaction of acid esters dihydric alcohol and more than 3 yuan of polyalcohol manufactures.
On the molecular weight of above-mentioned makrolon (methyl) acrylate, it is not particularly limited, such as weight can be enumerated Molecular weight is more than 500, preferably more than 1,000, more preferably above 2,000 scope.Makrolon (methyl) acrylate The upper limit of weight average molecular weight is not particularly limited, from the viewpoint of being controlled such that viscosity will not become too high, such as can To enumerate 100, less than 000, preferably 50, less than 000.Weight-average molecular as above-mentioned makrolon (methyl) acrylate Amount, from the viewpoint of mouldability is further improved, is preferably enumerated more than 2,000 and below 50,000, more preferably 5, 000~20,000.
Wherein, the weight average molecular weight of the makrolon in this specification (methyl) acrylate is to utilize gel permeation chromatography The value that method measures polystyrene as standard substance.
＜ multi-functional polyurethane (methyl) acrylate ＞
Multi-functional polyurethane (methyl) as long as acrylate main polymer chain has urethane bonds and end or side chain Material with (methyl) acrylate, is not particularly limited.Such polyurethane (methyl) acrylate for example can be with By using (methyl) acrylic acid by polyurethane obtained from the reaction as PPG, PEPA and PIC Oligomer is esterified and obtained.In addition, from the viewpoint of crosslinking, solidification is become good, polyurethane (methyl) acrylate The functional group number of every 1 molecule preferably enumerates 2~12.Form ionizing radiation curable resin combination used in superficial layer 2 In, in addition to containing above-mentioned makrolon (methyl) acrylate, polyurethane (methyl) acrylate can also be contained.Poly- ammonia Ester (methyl) acrylate can be used alone, and two or more can also be applied in combination.
The molecular weight of polyurethane (methyl) acrylate is not particularly limited, such as can enumerate weight average molecular weight 2,000 Above, more than 5,000 are preferably enumerated.The upper limit of the weight average molecular weight of polyurethane (methyl) acrylate is not particularly limited, from entering From the viewpoint of row control causes viscosity not become too high, such as less than 30,000 can be enumerated, preferably enumerate less than 10,000.
Wherein, the weight average molecular weight of the polyurethane in this specification (methyl) acrylate is to utilize gel permeation chromatography The value that polystyrene is measured as standard substance.
＜ silicone-based ionizing radiation curable resins ＞
As the ionizing radiation curable resin for forming superficial layer 2, by containing silicone-based ionizing radiation curable resin, The strip operation of thermoplastic resin film layer 30 in decorated resin products formed can be made become easy, and assign excellent design sense and Hand sense of touch.
As silicone-based ionizing radiation curable resin, it is not particularly limited, preferably enumerates acrylic acid silicone (methyl) third Olefin(e) acid ester, Silicone acrylates and silicone-modified polyurethane (methyl) acrylate, particularly preferred acrylic acid silicone (methyl) third Olefin(e) acid ester.Wherein, in the present invention, " acrylic acid silicone (methyl) acrylate " expression " in 1 molecule, acrylic resin The part of structure be replaced into siloxanes key (Si-O), and as side chain of the functional group in acrylic resin and/or master Chain end has the material of more than 2 (methyl) acryloxies ".In addition, " silicone (methyl) acrylate " expression " will gather Siloxanes has imported the modified silicon oil of (methyl) acryloyl group as the side chain of the silicone oil of main chain or two ends ".Below, to being adapted to Acrylic acid silicone (methyl) acrylate, silicone (methyl) acrylate and silicon as silicone-based ionizing radiation curable resin Ketone modified polyurethane (methyl) acrylate is described in detail.
(acrylic acid silicone (methyl) acrylate)
Acrylic acid silicone (methyl) acrylate is not particularly limited, as long as in 1 molecule, the knot of acrylic resin A part for structure is replaced into siloxanes key (Si-O) and as functional group at side chain and/or the main chain end of acrylic resin Material of the end with more than 2 (methyl) acryloxies (acryloxy or methacryloxy).As this third The example of olefin(e) acid silicone (methyl) acrylate, such as the side preferably enumerated disclosed in Japanese Unexamined Patent Publication 2007-070544 publications Chain has the structure of the acrylic resin of siloxanes key.
Acrylic acid silicone (methyl) acrylate used in the present invention for example can be by radical polymerization initiator In the presence of silicone-macromers and (methyl) acrylate monomer is occurred free-radical polymerized and is synthesized.As (methyl) third Olefin(e) acid ester monomer, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) can be enumerated Butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, glycidyl (methyl) acrylate etc..These (methyl) third Olefin(e) acid ester monomer can be used alone or 2 kinds are applied in combination.
Silicone-macromers for example can be by regarding n-BuLi or silanol lithium as polymerization initiator, making six alkyl rings Trisiloxanes carries out active anionic polymerization, recycles the silane containing free-radical polymerised unsaturated group to be blocked and closed Into.As silicone-macromers, it is adapted to using the compound shown in following formula (1).
Here, in formula (1), R1Represent the alkyl of carbon number 1~4, preferably methyl or normal-butyl.R2Represent having for 1 valency Machine group, preferably-CH=CH2,-C6H4- CH=CH2,-(CH2)3O (CO) CH=CH2Or-(CH2)3O(CO)C(CH3)= CH2。R3Each can be with identical or different, the alkyl or phenyl of the alkyl, preferably carbon number 1~4 of expression carbon number 1~6, More preferably methyl.In addition, n numerical value is not particularly limited, such as the number-average molecular weight of silicone-macromers is preferably 1,000 ~30,000, more preferably 1,000~20,000.
Acrylic acid silicone (methyl) acrylate obtained from above-mentioned raw materials can be used for example with following formula (2), (3) (4) construction unit shown in.
In formula (2), (3) and (4), R1、R3Implication and identical, the R in formula (1)4Represent hydrogen atom or methyl, R5Represent Alkyl or glycidyl in above-mentioned (methyl) acrylate monomer or there can be above-mentioned (methyl) acrylate monomer In alkyl or the functional group such as glycidyl alkyl, R6Represent the organic group with (methyl) acryloxy.It is above-mentioned Acrylic acid silicone (methyl) acrylate can be used alone or 2 kinds are applied in combination.
The molecular weight of above-mentioned acrylic acid silicone (methyl) acrylate can be determined by gpc analysis, and with standard The weight average molecular weight of polystyrene conversion is preferably 1, more than 000, more preferably 2, and more than 000.Acrylic acid silicone (methyl) third The upper limit of the weight average molecular weight of olefin(e) acid ester is not particularly limited, from being controlled such that viscosity will not become too high viewpoint and go out Hair, preferably 150, less than 000, more preferably 100, less than 000.From taking into account three-dimensionally shaped property, resistance to chemical reagents and marresistance From the viewpoint of, particularly preferably 2,000~100,000.
In addition, mean molecule quantity is preferably 100~2,500 between the crosslinking points of acrylic acid silicone (methyl) acrylate.Close The mean molecule quantity between crosslinking points, from preferably more than 100 from the viewpoint of three-dimensionally shaped property, from resistance to chemical reagents and marresistance Viewpoint sets out preferably less than 2,500.From the same viewpoint, it is average between the crosslinking points of acrylic acid silicone (methyl) acrylate Molecular weight is more preferably 100~1,500, more preferably 100~1,000.
(silicone (methyl) acrylate)
As silicone (methyl) acrylate, as long as using side chain of the polysiloxanes as the silicone oil of main chain or two ends The modified silicon oil of (methyl) acryloyl group has been imported, has been not particularly limited, 1 function or 2 function silicone (first can be used Base) acrylate, multifunctional (more than 3 functions) silicone (methyl) acrylate.
As 1 function or 2 function silicone (methyl) acrylate, existing known material can be used, as long as it is organic Group is (methyl) acrylic, the modified silicon oil with 1 to 2 organic group, is not particularly limited.In addition, change The structure of property silicone oil according to the bonding position of substituted organic group can be roughly divided into side chain type, two tip types, single tip type, The tip type of side chain two, but the bonding position of organic group is not particularly limited., can as such silicone (methyl) acrylate Meet that weight average molecular weight is preferably 1000~6000, is more preferably 3000~6000, functional equivalent's (Weight-average molecular with use Amount/functional group number) it is preferably 500~3000, the material of more preferably 1500~3000 condition.
In addition, as multifunctional (more than 3 functions) silicone (methyl) acrylic acid used in silicone (methyl) acrylate Ester, existing known material can be used, as long as organic group be (methyl) acrylic, have it is multiple, preferably 4 with Above, the modified silicon oil of more preferably 4~6 organic groups, is not particularly limited.In addition, the structure of modified silicon oil according to The bonding position of substituted organic group can be roughly divided into side chain type, two tip types, single tip type, the tip type of side chain two, but The bonding position of organic group is not particularly limited.As such silicone (methyl) acrylate, it can use and meet that weight is equal Molecular weight is preferably 3000~100000, is more preferably 10000~30000, functional equivalent's (weight average molecular weight/functional group number) Preferably 750~25000, it is more preferably the material of 3000~6000 condition.
Wherein, the weight average molecular weight of the silicone in this specification (methyl) acrylate is to utilize gel permeation chromatography will The value that polystyrene measures as standard substance.
(silicone-modified polyurethane (methyl) acrylate)
As silicone-modified polyurethane (methyl) acrylate, it is not particularly limited, can illustrates polyurethane with silicone Compound obtained from a part for the side chain of (methyl) acrylate is modified.Silicone-modified polyurethane (methyl) acrylate example Such as can be by making hydroxyl (methyl) acrylate and the silicone compounds with silanol base and the poly- ammonia with NCO Ester prepolymer reacts and obtained.
On the functional group number and molecular weight of silicone-modified polyurethane (methyl) acrylate, such as every 1 point can be enumerated The functional group number of son is 1~10, is preferably 2~8, is more preferably 3~6 and weight average molecular weight is 1000~50000, is preferably 3000~30000, it is more preferably 5000~10000 material.
Ratio as the silicone-based ionizing radiation curable resin in the ionizing radiation curable resin for forming superficial layer 2 Example, preferably enumerates 1~10 mass % or so, more preferably enumerates 1~5 mass % or so, further preferably enumerates 3~5 mass % Left and right.
＜ others additives ＞
, can be according to wishing what superficial layer 2 possessed in addition, for being formed in the hardening resin composition of superficial layer 2 Physical property coordinates various additives.As the additive, such as the improved weatherings such as ultra-violet absorber, light stabilizer can be enumerated Agent, wear resistance enhancer, polymerization inhibitor, crosslinking agent, infrared absorbent, antistatic additive, cementability enhancer, levelling agent, touch It is denatured imparting agent, coupling agent, plasticizer, defoamer, filler, solvent, colouring agent, wax etc..These additives can be from usual Appropriate selection uses in material.In addition, as ultra-violet absorber, light stabilizer, it can also use intramolecular that there is (first Base) polymerizable group such as acryloyl group reactive ultra-violet absorber, light stabilizer.Also, by coordinating wax, it can make Scratch resistance, wear resistance improve.As wax, the olefin waxes such as Tissuemat E (PE waxes) are preferably enumerated.In the case where coordinating wax, As the use level in hardening resin composition, preferably enumerate 0.1~5 mass % or so, more preferably enumerate 0.5~3 matter Measure % or so.
The thickness G T.GT.GT of ＜ superficial layers 2
The thickness after solidification for superficial layer 2, is not particularly limited, for example, can enumerate 0.01~200 μm, preferably 0.01~100 μm, more preferably 0.01~80 μm.By meeting the thickness of this scope, concave-convex can be more effectively shown Shape, possess excellent design sense and hand sense of touch.Also, design sense and hand sense of touch from not only cosmetic sheet are excellent, mouldability is also excellent From the viewpoint of different, the thickness is preferably shorter than 50 μm, more preferably 0.01~40 μm, particularly preferably 0.01~30 μm.Wherein, Such as shown in Fig. 1, Fig. 2 and Fig. 4, such as in the case where concaveconvex shape is formed by being embossed processing, from effectively showing Concaveconvex shape, from the viewpoint of possessing especially excellent design sense and hand sense of touch, it is excellent as the thickness after the solidification of superficial layer 2 Choosing enumerates 0.01~20 μm, more preferably 0.01~15 μm, more preferably 0.01~12 μm.Wherein, the thickness of superficial layer 2 Refer to the thickness of the convex portion of superficial layer 2.
The formation ＞ of ＜ superficial layers 2
In the first invention, as long as the solidfied material of the hardening resin composition of superficial layer 2 is to possess the side of concaveconvex shape Formula is formed on defined layer, and its specific method is not particularly limited.Concaveconvex shape is assigned as to superficial layer 2 Method, such as can enumerate：Implement embossing processing method, by formed superficial layer 2 resin combination be only coated on to be formed it is convex The part in portion simultaneously makes its method solidified etc..Such as from the viewpoint of fine concaveconvex shape is assigned, it is preferable to carry out embossing and adds The method (such as first method described later or second method) of work.In addition, from recess and the quality sense of convex portion and gloss occurs Change, from the viewpoint of obtaining the more distinct concave-convex design of contrast, preferably the resin combination for forming superficial layer 2 is only coated with In the method (such as third method described later) for forming the part (protuberance layer) of convex portion and solidifying it.
As the forming method of the superficial layer 2 with concaveconvex shape, following first method~3rd can be specifically enumerated Method.
First method：By substrate layer 1 and other layers being arranged as required to successively lamination, preparing has beyond superficial layer 2 Other layers of sheet material, embossing processing is implemented to the side of the stack surface layer 2 of the sheet material, is coated with afterwards for forming superficial layer 2 hardening resin composition, the method for solidifying the hardening resin composition.
Second method：By substrate layer 1 and other layers being arranged as required to successively lamination, preparing has beyond superficial layer 2 Other layers of sheet material, be coated with the side of the stack surface layer 2 of the sheet material for formed superficial layer 2 curable resin combine Thing, solidify the hardening resin composition, implement the method for embossing processing to the side of superficial layer 2 afterwards.
Third method：By substrate layer 1 and other layers being arranged as required to successively lamination, preparing has beyond superficial layer 2 Other layers of sheet material, be only coated with the part of formation convex portion of the side of the stack surface layer 2 of the sheet material for forming surface The hardening resin composition of layer 2, the method for solidifying the hardening resin composition.
On the other hand, in the case where using resin film as the superficial layer 2 of the second invention, under superficial layer 2 Layer superimposed layer resin film, processing is embossed on resin film, thus, it is possible to form the superficial layer 2 with concaveconvex shape.
In addition, in the second invention, in the case where forming superficial layer 2 using hardening resin composition, as long as solidification The solidfied material of property resin combination is formed in a manner of possessing concaveconvex shape on defined layer, and its specific method does not have There is special limitation.As the method to the imparting concaveconvex shape of superficial layer 2, such as can enumerate：Implement the method for embossing processing, incite somebody to action The resin combination for forming superficial layer 2 is only coated on the part to form convex portion and makes its method solidified etc., is preferable to carry out being embossed The method of processing.
In the second invention, in the case where forming superficial layer 2 using hardening resin composition, as with concave-convex The forming method of the superficial layer 2 of shape, it can specifically enumerate above-mentioned first method~third method.
In the first invention and the second invention, for will be coated on for the hardening resin composition for forming superficial layer 2 Method on defined layer is not particularly limited, for example, for above-mentioned first method or second method when, intaglio plate can be enumerated Coating, rod painting, roller coat, deposited, the point type coating of inverse roller coat etc., preferably enumerate gravure coating.In addition, for above-mentioned third method when, Can enumerate silk-screen printing, the printing of intaglio plate protuberance, rotary screen printing, described in Japanese Unexamined Patent Publication 2002-240078 publications It is molded the printings or rubbing method etc. such as plate cylinder method.
Electronics is irradiated to the hardening resin composition (uncured resin layer) that is coated with defined layer is so operated The ionizing rays such as ray, ultraviolet, make the resin composition, form superficial layer 2.Here, used as ionizing ray In the case of electron ray, its accelerating potential can be suitably selected according to the thickness of used resin and layer, can generally arrange Lift 70~300kV of accelerating potential or so.
Wherein, when irradiating electron ray, the more highly transmissive ability of accelerating potential more increases, thus using because of electron ray and In the case that the base material of deterioration is as substrate layer, selected accelerating potential causes the transmission depth of electron ray and the thickness of resin bed Be substantially equal, irradiated thus, it is possible to suppress unnecessary electron ray to substrate layer, can will because excess electrons ray and caused by Base material degradation inhibiting in Min..
In addition, the crosslink density of exposure dose preferred resin layer reaches the amount of saturation, generally 5~300kGy (0.5~ 30Mrad), selected preferably in the range of 10~50kGy (1~5Mrad).
Also, be not particularly limited as electronic radial source, for example, can use examine croft-Wa Erdun types, Fan De Lattice pressgang type, resonance transformer type, insulating core transformer typ or linear pattern, the various electron rays such as that meter of type, high-frequency type add Fast device.
In the case where using ultraviolet as ionizing ray, the light of ultraviolet of the radiation comprising 190~380nm of wavelength .It is not particularly limited as ultraviolet source, such as high-pressure sodium lamp, low pressure mercury lamp, metal halogen etc., carbon arc lamp can be enumerated Deng.
[thermoplastic resin film layer 30]
In the first invention, thermoplastic resin film layer 30 is to suppress in the vacuum forming or injection moulding of cosmetic sheet The concaveconvex shape deformation of superficial layer 2 or the layer for disappearing and setting.Thermoplastic resin film layer 30 is with can be from cosmetic sheet (superficial layer 2) The state stack of stripping, it is that the layer peeled off afterwards is being integrally formed with moulding resin.
Wherein, in the present invention, " can peel off " of thermoplastic resin film layer be refer to by thermoplastic resin film layer from Superficial layer with concaveconvex shape is peeled off, in particular to can peeled off and concaveconvex shape is not destroyed.For example, according to JIS In assay method as defined in Z0237 " 10. bonding forces determine 10.4.1 and tear off bonding force for 180 ° of breadboard ", by surface When bonding force when layer is torn off with thermoplastic resin film layer is 0.01~20N/25mm or so, can fully it peel off.It is viscous as this With joint efforts, preferably enumerate 0.01~20N/25mm or so, more preferably 0.02~10N/25mm or so, more preferably 0.05~ 5N/25mm or so.Wherein, when the bonding force is less than 0.01N/25mm, sometimes before the shaping of cosmetic sheet, shaping it is medium when heat Plastic resin film layer is unexpectedly peeled off from superficial layer, in addition, when more than 20N/25mm, although according to thermoplastic resin film layer The tensile strength of thickness and resin etc. is different, but when thermoplastic resin film layer is peeled off, sometimes thermoplastic resin film layer Breakage, one part are remained on forming resin layer, and a part for superficial layer pulls off together with thermoplastic resin film layer, surface Layer is damaged or deforms.
In the first invention, thermoplastic resin film layer 30 and superficial layer 2 can direct lamination, can also fold between these layers Layer has other layers.In the case of thermoplastic resin film layer 30 and 2 direct lamination of superficial layer, thermoplastic resin film layer 30, which turns into, protects Protect the concavo-convex protective layer 3 of the concaveconvex shape of superficial layer 2.
In the first invention, in the case of superficial layer 2 and 30 direct lamination of thermoplastic resin film layer, preferred thermoplastic tree Adipose membrane layer 30 fills at least a portion of the recess of the concaveconvex shape of superficial layer 2.By thermoplastic resin film layer 30 by surface The recess landfill of the concaveconvex shape of layer 2, it can further improve the recessed of protection superficial layer 2 caused by thermoplastic resin film layer 30 The function of convex form.
In the first invention, as the recess of the concaveconvex shape of superficial layer 2 is filled by thermoplastic resin film layer 30 Method, such as can enumerate：By extrusion molding or heat lamination, in a manner of the recess of the concaveconvex shape of superficial layer 2 to be filled Multilayer thermoplastic resin film layer 30.In the cosmetic sheet of the first invention, superficial layer 2 by hardening resin composition solidfied material shape Into.Therefore, compared with the cosmetic sheet that surface possesses the thermoplastic resin film provided with concaveconvex shape, can suppress by heat lamination or During extrusion molding multilayer thermoplastic resin film layer 30 because of caused by heating concaveconvex shape deformation.
In addition, in the cosmetic sheet of the first invention, the concave-convex of superficial layer 2 is protected by thermoplastic resin film layer 30 Shape, therefore compared with cosmetic sheet of the resin bed by being made up of the solidfied material of curable resin to protect concaveconvex shape, injection Mouldability when shaping and preforming (vacuum forming) carried out before it is also excellent.Also, due to that can be adequately suppressed The deformation of concaveconvex shape and operability when peeling off is good, thus even in the thickness of increase thermoplastic resin film layer 30 In the case of, with using the solidfied material of curable resin, compared with the situation of the protective layer of concaveconvex shape, mouldability is not easy to be damaged. Therefore, the cosmetic sheet of the first invention is also suitable for the cosmetic sheet of the high three-dimensionality formation of demand.
In the first invention, cause thermoplastic resin film layer 30 and superficial layer 2 with the shape of cosmetic sheet from adjustment adhesive strength State is closely sealed, be integrally formed with moulding resin after be easily peeled off from the viewpoint of, thermoplastic resin film layer 30 is preferably by being extruded into Type lamination.
In the first invention, in the case that lamination has other layers between thermoplastic resin film layer 30 and superficial layer 2, this its His layer and thermoplastic resin film layer 30 can be used as concavo-convex protective layer 3 to play function.As other layers, such as can enumerate aftermentioned Bonding adhesive linkage 31, release layer 32 etc..
In the first invention, between thermoplastic resin film layer 30 and superficial layer 2 in the case of lamination bonding adhesive linkage 31, From the viewpoint of the concaveconvex shape deformation for suppressing the superficial layer 2 when thermoplastic resin film layer 30 is formed or disappearing, preferably in shape Into after bonding adhesive linkage 31 described later, by the bonding force or the ready-made thermoplasticity of bonding force lamination that bond adhesive linkage 31 Resin film layer 30.In the case where bonding adhesive linkage 31 is formed by bonding agent, bonding adhesive linkage 31 can be by with bumps Coating adhesive on the superficial layer 2 of shape and formed.Therefore, when forming bonding adhesive linkage 31, it is not necessary to extrusion molding or heat Heating caused by lamination.Therefore, in the case where bonding adhesive linkage 31 is formed by bonding agent, superficial layer can suitably be maintained 2 fine concaveconvex shape, and it is capable of the thermoplastic resin film layer 30 of concaveconvex shape of the lamination for protecting superficial layer 2.
In the first invention, as the thermoplastic resin for forming thermoplastic resin film layer 30, it is not particularly limited, Ke Yilie Lift：Acrylonitrile-butadiene-styrene resin (is also denoted as " ABS resin ") sometimes below；Acrylonitrile-styrene-acrylic acid Ester resin；Acrylic resin；The polyolefin-based resins such as polypropylene, polyethylene；Polycarbonate resin；Vinyl chloride-based resin；Poly- pair Polyester resin such as PET (PET) resin, polybutylene terephthalate (PBT) (PBT) resin etc..Thermoplastic resin Fat can individually contain a kind, can also contain two or more.
In the first invention, when manufacturing decorated resin products formed by injection moulding, it is known that mainly in injecting resin Injection site, it some times happens that because the injecting resin of high temperature causes the so-called of the meltings such as superficial layer, the patterned layer of cosmetic sheet The phenomenon of cast gate flowing, damages design.In order to reduce cast gate flowing, the heat for being applied to cosmetic sheet is emitted to injection molding Former (side contacted with the surface of cosmetic sheet) be effective, but filled as the first invention as final residue Adorn between superficial layer, patterned layer and the former of the layer in synthetic resin, the heat finally peeled off from decorated resin products formed be present In the case of the cosmetic sheet of plastic resin film layer, the heat being provided with to superficial layer, patterned layer is difficult to be emitted to former, easily hair The danger of raw cast gate flowing.It is logical after cosmetic sheet is heated in mould, soften in addition, in injection moulding simultaneously in decorative method Cross vacuum attraction by cosmetic sheet it is preforming in the case of, sometimes result in thermoplastic resin film layer and overbate, be arranged at the moon The suction hole suction of the vacuum attraction of mould and hole is blocked or the residue of film is accumulated in hole.From suppressing these problems Viewpoint is set out, and preferred thermoplastic resin film layer is the layer containing non-crystalline polyester resin.Due to non-crystalline polyester resin Heat resistance is more excellent than polyethylene etc., it is thus possible to which the generation or suppression thermoplastic resin film layer for alleviating cast gate flowing are attracted hole Suction.Also, due to non-crystalline polyester resin than crystalline polyester resin more rich in flexibility, thus it also can ensure that decoration The three-dimensionally shaped property of piece.
In the first invention, as non-crystalline polyester resin, preferably using amorphism polyethylene terephthalate Ester (PET).As amorphism PET, the resin known to as A-PET or PET-G can be generally used.
In the first invention, as the thickness of thermoplastic resin film layer 30, it is not particularly limited, preferably enumerates 5~300 μm Left and right, it is more preferably 5~100 μm or so.Wherein, such as shown in Fig. 1, Fig. 2 and Fig. 4, for example, by be embossed processing formed it is recessed In the case of convex form, from the viewpoint of effectively showing concaveconvex shape, possessing especially excellent design sense and hand sense of touch, It is preferred that enumerate 5~100 μm or so, more preferably 20~50 μm or so.In addition, thermoplastic resin film layer 30 can be by multilayer structure Into.
(bonding adhesive linkage 31)
In the first invention, bonding adhesive linkage 31 is set as needed between thermoplastic resin film layer 30 and superficial layer 2 The layer put.Bonding adhesive linkage 31 is formed by bonding agent or adhesive.In the first invention, have in lamination and glued by what bonding agent was formed In the case of closing adhesive linkage 31, bonding adhesive linkage 31 fills the recess of the concaveconvex shape of superficial layer 2.
In the first invention, as bonding agent used in bonding adhesive linkage 31, as long as can be with by the recessed of superficial layer 2 The mode of convex form landfill is coated with and can be together with thermoplastic resin film layer 30 from the material of the sur-face peeling of superficial layer 2 , it is not particularly limited, preferably using curable resin.As curable resin, such as polyurethane series bonding can be enumerated Agent, acrylic acid series bonding agent, epoxy bonding agent, rubber series bonding agent etc., wherein, filled from being also able to maintain that in injection moulding Point bonding force aspect and can consider from sur-face peeling of superficial layer 2 etc., preferred urethane adhesive.Its In, as such urethane adhesive, there are biliquid curable polyurethane resin system bonding agent etc., biliquid curable polyurethane Resin system bonding agent be make use of containing the various hydroxy-containing compounds such as PPG, PEPA, acrylic polyol, With the biliquid curable polyurethane tree of the various polyisocyanate compounds such as toluene di-isocyanate(TDI), hexamethylene diisocyanate The bonding agent of fat.
In addition, in the first invention, in the case where bonding adhesive linkage 31 is using adhesive, can use in above-mentioned heat The bonding sheet of adhesive is coated with plastic resin film layer 30.As such bonding sheet, can enumerate in common polypropylene Material of acrylic adhesive etc. is coated with base material.
In the first invention, as bonding adhesive linkage 31 thickness, be not particularly limited, preferably enumerate 5~70 μm or so, More preferably 15~60 μm or so.Wherein, the thickness for bonding adhesive linkage 31 is layer (superficial layer 2 or the demoulding for being located in bottom The thickness of part on the convex portion of layer 32).
In the first invention, in the case where forming bonding adhesive linkage 31 by bonding agent, bonding adhesive linkage 31 is by locating Above-mentioned bonding agent is coated with the layer (superficial layer 2 or release layer 32) of bonding adhesive linkage 31 bottom and is formed.Specifically, it is sharp With gravure coating, rod painting, roller coat, inverse roller coat applies, point type applies the methods of the surface that bonding agent is coated on superficial layer 2 (had It is the surface of release layer 32 when having a release layer 32).
[the concavo-convex protective layer 3 of the second invention]
The concavo-convex protective layer 3 of second invention is the layer set on superficial layer 2 with the state contacted with the face of superficial layer 2, with Can be the layer peeled off after being integrally formed with moulding resin from the state stack of the interface peel with superficial layer 2.In the second invention In, concavo-convex protective layer 3 possesses the and of adhesive linkage 31 of the recess of the concaveconvex shape of landfill surface layer 2 successively from the side of superficial layer 2 Peel off film layer 33.
In the second invention, the adhesive linkage 31 of concavo-convex protective layer 3 is formed by bonding agent, can be by with concaveconvex shape Superficial layer 2 on coating adhesive and formed.Therefore, when forming adhesive linkage, it is not necessary to as disclosed in above-mentioned patent document 1 Cushion heated like that because of caused by extrusion molding or heat lamination.Therefore, in the second invention, table can suitably be maintained The fine concaveconvex shape of surface layer 2 and the concavo-convex protective layer 3 that the concaveconvex shape for protecting superficial layer 2 can be formed.
(adhesive linkage 31 of the second invention)
As bonding agent used in the adhesive linkage 31 of the concavo-convex protective layer 3 of the second invention, as long as can be with by superficial layer 2 Concaveconvex shape landfill mode be coated with and can together with peeling off film layer 33 from the material of the sur-face peeling of superficial layer 2 i.e. Can, it is not particularly limited, preferably using curable resin.As curable resin, for example, can enumerate urethane adhesive, Acrylic acid series bonding agent, epoxy bonding agent, rubber series bonding agent etc., wherein, also it is able to maintain that fully from injection moulding Bonding force aspect and can consider from sur-face peeling of superficial layer 2 etc., preferred urethane adhesive.Wherein, As such urethane adhesive, there are biliquid curable polyurethane resin system bonding agent etc., biliquid curable polyurethane tree Fat system bonding agent be make use of containing the various hydroxy-containing compounds such as PPG, PEPA, acrylic polyol and The biliquid curable polyurethane resin of the various polyisocyanate compounds such as toluene di-isocyanate(TDI), hexamethylene diisocyanate Bonding agent.
In the second invention, as the thickness of adhesive linkage 31, be not particularly limited, preferably enumerate 5~70 μm or so, it is more excellent Elect 15~60 μm or so as.Wherein, the thickness of adhesive linkage 31 be located in bottom layer (superficial layer 2 or release layer 32) it is convex The thickness of part on portion.
In the second invention, adhesive linkage 31 can be by layer (superficial layer 2 or the release layer under adhesive linkage 31 32) above-mentioned bonding agent is coated with and is formed.Specifically, using gravure coating, rod painting, roller coat, inverse roller coat applies, point type applies Bonding agent is coated on the surface (being the surface of release layer 32 when with release layer 32) of superficial layer 2 by the methods of applying.
(the stripping film layer 33 of the second invention)
In the second invention, it is concavo-convex protective layer 3 to be formed together with adhesive linkage 31, in order to suppress decorating to peel off film layer 33 The concaveconvex shape deformation of superficial layer 2 or the layer for disappearing and setting when the vacuum forming or injection moulding of piece.
As the raw material of the stripping film layer 33 of the second invention, it is not particularly limited, such as preferred illustration and the first invention The thermoplastic resin that is illustrated in thermoplastic resin film layer 30 material same (also including non-crystalline polyester resin).
As the thickness of the stripping film layer 33 of the second invention, be not particularly limited, preferably enumerate 5~100 μm or so, it is more excellent Elect 20~50 μm or so as.
(release layer 32)
In the first invention and the second invention, release layer 32 is to improve thermoplastic resin film layer 30 and superficial layer 2 Fissility etc., the layer being arranged as required to.Release layer 32 can contact setting with superficial layer 2.In the present invention, have in lamination de- In the case of mold layer 32, release layer 32 fills the recess of the concaveconvex shape of superficial layer 2.In addition, release layer 32 with by be bonded Dosage form into the lamination of bonding adhesive linkage 31 in the case of, the present invention cosmetic sheet in, release layer 32 and bonding adhesive linkage 31 will The recess landfill of the concaveconvex shape of superficial layer 2.
As the raw material for forming release layer 32, as long as it can be carried out in a manner of the concaveconvex shape of superficial layer 2 is filled It is coated with and can not especially be limited together with thermoplastic resin film layer 30 from the material of the sur-face peeling of superficial layer 2 Fixed, release layer 32 is preferably formed by the solidfied material of ionizing radiation curable resin combination.Thereby, it is possible to more effectively suppress The deformation or disappearance of the concaveconvex shape of superficial layer 2 when vacuum forming or injection moulding, decorated resin products formed can be assigned excellent Different design sense and hand sense of touch.
Ionizing radiation curable resin ＞ in ＜ release layers 32
Species, preferable material on the ionizing radiation curable resin for forming release layer 32 etc., and for shape Material into above-mentioned superficial layer 2 is identical.It is above-mentioned on being illustrated in superficial layer 2 one especially in ionising radiation resin (1) combination of ionizing radiation curable resin and the ionizing radiation curable resin of above-mentioned (2), not only possesses suppression in vacuum The concaveconvex shape deformation of superficial layer 2 or the effect of disappearance when shaping or injection moulding, can also possess integral with moulding resin Stripping easiness when being peeled off after shaping, thus be adapted to use in release layer 32.As the ionization spoke in release layer 32 Penetrate curable resin, preferably 3 function pentaerythritol acrylates.In addition, the ionizing radiation curable for forming release layer 32 Resin can be resin of the same race with the ionizing radiation curable resin for forming above-mentioned superficial layer 2, or not of the same race Resin.
＜ others adding ingredients ＞
For being formed in the ionizing radiation curable resin combination of release layer 32, except containing ionizing radiation curable tree Beyond fat, in order to improve mouldability etc., other resin components can also be contained as needed.Consolidate as such ionising radiation Resin component beyond the property changed resin, such as can enumerate：Acrylic resin；The Pioloform, polyvinyl acetals such as polyvinyl butyral resin (butyral resin)；The polyester resin such as polyethylene terephthalate, polybutylene terephthalate (PBT)；Vinyl chloride resin；It is poly- Urethane resin；The polyolefin such as polyethylene, polypropylene；The phenylethylene resin series such as polystyrene, α-methylstyrene；Polyamide；It is poly- Carbonic ester；The acetal resins such as polyoxymethylene；The fluorine resins such as ethylene-tetrafluoroethylene copolymer；Polyimides；PLA；It is poly- Vinyl acetal resin；The thermoplastic resins such as liquid crystalline polyester resin.These resin components can be used alone, also may be used So that two or more to be applied in combination.
Release layer 32, can also be by silicone-based tree in addition to ionizing radiation curable resin combination can be used to be formed Fat, fluorine resin, acrylic resin (such as including acrylic acid-melamine series resin), polyester based resin, polyolefin Resin, polystyrene resin, polyurethane series resin, cellulose-based resin, Chlorovinyl-acetate vinyl acrylic copolymer resin, The thermoplastic resins such as nitrocotton, formed the thermoplastic resin monomer copolymer or utilization (methyl) acrylic acid or poly- ammonia The resin that ester forms these resin modifieds is used alone to be formed or used and forms the resin combination of a variety of mixing.Its In, preferably acrylic resin, polyester based resin, polyolefin-based resins, polystyrene resin, the monomer for forming these resins Copolymer and to they carry out it is polyurethane-modified and formed resin, more specifically, can enumerate：Individually Acrylic acid-melamine series resin, the composition containing acrylic acid-melamine series resin, by polyester based resin with to ethene Polyurethane-modified and the resin mixing that is formed resin combination is carried out with the copolymer of acrylic acid, by acrylic resin and benzene Resin combination of emulsion mixing of the copolymer of ethene and acrylic acid etc..Among those, particularly preferably by independent propylene Acid-melamine series resin or the composition composition release layer containing more than the mass % of acrylic acid-melamine series resin 50 32。
In the resin combination for forming release layer 32, it may be considered that it is desirable that the possessed physical property of release layer 32 and coordinate each Kind additive.As the additive, such as the improved weathering such as ultra-violet absorber, light stabilizer agent, wear-resistant can be enumerated Property enhancer, polymerization inhibitor, crosslinking agent, infrared absorbent, antistatic additive, cementability enhancer, levelling agent, thixotropy assign Agent, coupling agent, plasticizer, defoamer, filler, solvent, colouring agent etc..These additives can be appropriate from conventional material Selection uses.In addition, as ultra-violet absorber, light stabilizer, it can also use intramolecular that there is (methyl) acryloyl group etc. Reactive ultra-violet absorber, the light stabilizer of polymerizable group.
As the thickness of release layer 32, it is not particularly limited, preferably enumerates 1~40 μm or so, more preferably 5~15 μm left side It is right.Wherein, the thickness of release layer 32 is the thickness of the part on the convex portion of superficial layer 2.
Release layer 32 can be formed by being coated with above-mentioned resin combination on superficial layer 2.Specifically, utilize The resin combination is coated on the surface of superficial layer 2 i.e. by the methods of gravure coating, rod painting, roller coat, inverse roller coat apply, point type coating Can.
[priming coat 4]
In the first invention and the second invention, priming coat 4 is in order to which fine split occurs in the extension being not easy in superficial layer 2 Line or albefaction etc., as needed between substrate layer 1 and superficial layer 2, in the case of provided with patterned layer 5 in patterned layer 5 and table The layer of setting such as between surface layer 2 and/or between substrate layer 1 and patterned layer 5.
From the viewpoint of adaptation of the superficial layer 2 with the layer under it is improved, preferably in the lower section close to superficial layer 2 (in the case where resin bed 7 is formed by curable resin in the lower section close to resin bed 7) sets priming coat 4.
As the ground coating composition for forming priming coat 4, preferably with polyurethane resin, (methyl) acrylic resin, (methyl) Acrylic acid-polyurethane copolymer resin, vinyl chloride vinyl acetate copolymer, polyester resin, butyral resin, chlorination poly- third Alkene, haloflex etc. are the composition of adhesive resin, and these resins can be used alone, or mixing two or more. Among these, preferably polyurethane resin, (methyl) acrylic resin and (methyl) acrylic acid-polyurethane copolymer resin.
As polyurethane resin, it is host, using isocyanates as crosslinking agent (solidification that can use using polyalcohol (polyalcohol) Agent) polyurethane.As polyalcohol, the material in molecule with more than 2 hydroxyls can be used, for example, it is PEPA, poly- Ethylene glycol, polypropylene glycol, acrylic polyol, PPG etc..As above-mentioned isocyanates, can use has in molecule The aromatic isocyanates such as the multicomponent isocyanates of more than 2 NCOs, 4,4- methyl diphenylene diisocyanates or Hexamethylene diisocyanate, IPDI, hydrogenated toluene diisocyanate, the isocyanide of hydrogenated diphenyl methane two The aliphatic such as acid esters (or alicyclic) isocyanates.Also, polyurethane resin can also be mixed with butyral resin and formed.
Complexity, thing from the adaptation with the superficial layer 2 after crosslinking, by being interacted after the lamination of superficial layer 2 Property, from the aspect of mouldability, acrylic polyol or PEPA preferably as polyalcohol, with six Asias as crosslinking agent The combination of methyl diisocyanate, 4,4- methyl diphenylene diisocyanates, particularly preferably by acrylic polyol and six methylenes Group diisocyanate is applied in combination.
As (methyl) acrylic resin, homopolymer, two or more different (first of (methyl) acrylate can be enumerated Base) acrylate monomer copolymer or (methyl) acrylate and the copolymer of other monomers, specifically, be adapted to use Including poly- (methyl) methyl acrylate, poly- (methyl) ethyl acrylate, poly- (methyl) propyl acrylate, poly- (methyl) acrylic acid fourth Ester, (methyl) methyl acrylate-(methyl) butyl acrylate copolymer, (methyl) ethyl acrylate-(methyl) acrylic acid fourth Ester copolymer, ethene-(methyl) methyl acrylate copolymer, styrene-(methyl) methyl acrylate copolymer etc. contains (first Base) homopolymer of acrylate or (methyl) acrylic resin of copolymer.
As (methyl) acrylic acid-polyurethane copolymer resin, such as preferred acrylic acid-polyurethane (polyester-polyurethane) Block copolymerization system resin.As curing agent, above-mentioned various isocyanates can be used.Acrylic acid-polyurethane (the poly- ammonia of polyester Ester) block copolymerization system resin is preferably as needed by acrylic/polyurethane ratio (mass ratio) preferably 9/1~1/9, more preferably 8/ 2~2/8 scope is adjusted.
Thickness on priming coat 4 is not particularly limited, such as can enumerate 0.5~20 μm or so, be preferably 1~5 μm.
Priming coat 4 can use ground coating composition to pass through gravure coating, intaglio plate reversion coating, intaglio offset coating, rotation Coating, roller coat, inverse roller coat are applied, contact coating, wheeled coating (Wheeler coat), dip-coating, the full coat using silk-screen printing, silk The common coating methods such as rod coating, curtain coating coating, point type coating, curtain coating, bristle coating, spraying or transfer coating process shape Into.Here, transfer coating process is that priming coat, the film of adhesive linkage are formed on thin sheet material (film base material), is covered in dress afterwards The method in the layer surface as object in spike.
[patterned layer 5]
In the first invention and the second invention, patterned layer 5 can in order to cosmetic sheet is assigned it is ornamental, as needed in base Between material layer 1 and superficial layer 2 or side opposite with superficial layer 2 of substrate layer 1 etc. is set.In the case of provided with priming coat 4 According to need between shielding layer and superficial layer 2 etc. between substrate layer 1 and priming coat 4 or in the case of provided with shielding layer Set.As shown in fig. 6, patterned layer 5 can set multilayer.
Patterned layer 5 for example can be the layer that desired pattern is formd using ink composite.As formation patterned layer 5 Used ink composite, it can use and colouring agents such as pigment, dyestuff, extender pigment, molten are suitably mixed with adhesive The composition of agent, stabilizer, plasticizer, catalyst, curing agent etc..
As adhesive used in ink composite, it is not particularly limited, such as polyurethane resin, chloroethene can be enumerated Alkene/vinyl acetate copolymer resin, vinyl chloride/vinyl acetate/acrylic copolymer resin, chlorinated polypropylene, third Olefin(e) acid resin, polyester resin, polyamide, butyral resin, polystyrene resin, Nitro cellulose resin, cellulose acetate Resin etc..These adhesives can be used alone, and two or more can also be applied in combination.
As colouring agent used in ink composite, it is not particularly limited, such as can enumerates：Carbon black (black), iron The inorganic pigments such as black, titanium white, stibium trioxide, chrome yellow, titan yellow, iron oxide red, cadmium red, ultramarine, cobalt blue；Quinacridone is red, isoindoline Organic pigment or the dyestuffs such as ketone Huang, phthalocyanine blue；The metallic pigments that aluminium, brass etc. are made up of flakey paillon foil；Cladding titanium dioxide Mica, pearly-lustre (pearl) pigment being made up of flakey paillon foil such as basic lead carbonate etc..
Also it is not particularly limited for the pattern formed by patterned layer 5, such as wood grain decorative pattern, marbling can be enumerated (such as calcareous tufa marbling) etc. imitate the bag decorative pattern of rock surface, the cloth decorative pattern for imitating woven design or cloth-like decorative pattern, Patch block decorative pattern, decorative pattern of laying bricks etc. or by they it is compound inlay wood grain, piece together the decorative patterns such as pattern, or can also be Monochrome is without decorative pattern (so-called full up).These patterns can be by using the work of common yellow, red, blueness and black The polychrome printing of skill pigment and formed, the polychrome using characteristic that can also be by each color version of composition of preparation decorative pattern to carry out Printing etc. and formed.
The thickness of patterned layer is not particularly limited, such as can enumerate 1~30 μm, preferably 1~20 μm.
Also, patterned layer 5 can also be metal film layer.As the metal of formation metal film layer, such as can enumerate Tin, indium, chromium, aluminium, nickel, copper, silver, gold, platinum, zinc and contain at least one kind of alloy in them etc..The formation side of metal film layer Method is not particularly limited, such as can enumerate and use the vapour deposition methods such as above-mentioned metal, vacuum vapour deposition, sputtering method, ion plating Method etc..Metal film layer can be set in entire surface, can also partly be set.It is in addition, closely sealed with adjacent layer in order to improve Property, the priming coat of known resin can also be set using in the front of metal film layer or the back side.
[shielding layer]
In the first invention and the second invention, shielding layer be in order to suppress the color change of substrate layer 1 or it is irregular and in base Between material layer 1 and superficial layer 2, when provided with priming coat 4 between substrate layer 1 and priming coat 2 or when provided with patterned layer 5 The layer being arranged as required between substrate layer 1 and patterned layer 5.
Shielding layer to the tone or pattern of cosmetic sheet due to having undesirable effect and set to suppress substrate layer, so logical It is often formed as the layer of body color.
Shielding layer use be suitably mixed with adhesive the colouring agents such as pigment, dyestuff, extender pigment, solvent, stabilizer, The ink composite of plasticizer, catalyst, curing agent etc. and formed.The ink composite for forming shielding layer can be from above-mentioned figure Appropriate selection uses in material used in pattern layer.
The thickness of shielding layer is typically set at 1~20 μm or so, is preferably formed into so-called full coat printing layer.
Shielding layer passes through intaglio printing, offset printing, silk-screen printing, the printing using the transfer by transfer sheet, ink-jet print The common printing processes such as brush；Gravure coating, intaglio plate reversion coating, intaglio offset coating, spin coated, roller coat, inverse roller coat apply Etc. the formation such as common coating method.[transparent resin layer 6]
In the first invention and the second invention, transparent resin layer 6 be in order to improve resistance to chemical reagents and marresistance and in base Scheming between material layer 1 and superficial layer 2, when provided with priming coat 4 between substrate layer 1 and priming coat 4, when provided with patterned layer 5 In priming coat 4 and patterned layer 5 between pattern layer 5 and superficial layer 2 or when being sequentially provided with priming coat 4 and patterned layer 5 on substrate layer 1 Between etc. the layer that is arranged as required to.Transparent resin layer 6 is in by the insert-molding method cosmetic sheet integrated with moulding resin It is the layer being preferably provided with.
, can be according to transparent, three-dimensionally shaped property, shape stability, resistance to as the resin component for forming transparent resin layer 6 Medicine etc. suitably selects, usually using thermoplastic resin.As thermoplastic resin, it is not particularly limited, such as can uses The vistanexes such as acrylic resin, polypropylene, polyethylene, polycarbonate resin, ABS resin, polyethylene terephthalate Polyester resin, the vinyl chloride resins such as ester (PET), PEN (PEN) etc..Among these thermoplastic resins, From viewpoints such as resistance to chemical reagents, marresistances, acrylic resin, vistanex, polycarbonate resin, polyester are preferably enumerated Resin, more preferably acrylic resin, polyester resin, further preferred polyester resin.
, can be as needed to list in order to improve the adaptation of other layers contacted with face for transparent resin layer 6 The surface treatment physically or chemically of oxidizing process or further provided for contouring method etc. is implemented on face or two sides.These surface treatments physically or chemically It is same with the surface treatment that substrate layer is implemented.
It is not particularly limited for the thickness of transparent resin layer 6, such as 10~200 μm can be enumerated, preferably 15~150 μ m。
Transparent resin layer 6 can via bonding agent lamination, can also not via bonding agent direct lamination.Via bonding In the case of agent lamination, as used bonding agent, such as polyester based resin, polyethers system resin, polyurethane series can be enumerated Resin, epoxy system resin, phenolic resin system resin, polyamide series resin, polyolefin-based resins, polyvinyl acetate system resin, Cellulose-based resin, (methyl) acrylic resin, polyimides system resins, amino resins, rubber, silicon system resin etc..In addition, In the case of not via bonding agent lamination, it can be carried out using the methods of extrusion molding, interlayer laminating, lamination methods.
[resin bed 7]
In the first invention, resin bed 7 is to improve the purpose of the marresistance of decorated resin products formed, weatherability etc. Deng and as needed in the layer set close to the lower section of superficial layer 2 (side opposite with thermoplastic resin film layer 30).On surface The concaveconvex shape of layer 2 is by the convex portion that partly sets and the recess of the lower floor of exposing surface layer 2 is formed between raised part feelings Under condition, resin bed 7 is preferably provided with.
As the resin for the resin bed 7 for forming the first invention, it is not particularly limited, curable resin, thermoplastic can be enumerated Property resin etc..As curable resin, thermosetting resin, ionizing radiation curable resin etc., preferably ionising radiation can be enumerated Curable resin.As thermosetting resin and the concrete example of ionizing radiation curable resin, can illustrate and above-mentioned [superficial layer 2] the illustration identical material in.In addition, as thermoplastic resin, can illustrate with above-mentioned [thermoplastic resin film layer 30] Illustration identical material.In the case where resin bed 7 is thermoplastic resin, as resin bed 7, preferably using thermoplastic resin Film.
In the case of provided with resin bed 7, in order to improve adaptation between resin bed 7 and the layer being disposed below etc., Bond layer (not shown) can be set close to the lower section of resin bed 7 (side opposite with superficial layer 2) as needed.Especially It is in the case where using thermoplastic resin film as resin bed 7, bond layer can be set.As the tree for forming bond layer Fat, it can illustrate and the illustration identical material in [back side adhesive linkage] described later.
It is not particularly limited for the thickness of resin bed 7, such as 30~300 μm μm can be enumerated, preferably 50~200 μm.
[back side adhesive linkage]
In the first invention and the second invention, bleed-through face adhesive linkage (not shown) be in order to decorated resin products formed into Improved during type with the adaptation of moulding resin and in the back side of substrate layer 1 (face of the side opposite with superficial layer 2) as needed The layer of setting.
Back side adhesive linkage can with moulding resin used in decorated resin products formed accordingly using thermoplastic resin or Curable resin.
As formed back side adhesive linkage used in thermoplastic resin, such as acrylic resin can be enumerated, acrylic acid changes Property vistanex, chlorinated polyolefin resin, vinyl chloride/vinyl acetate copolymer, TPU, thermoplastic poly Ester resin, polyamide, rubber series resin etc..These thermoplastic resins can be used alone, can also be by two or more It is applied in combination.
In addition, as forming thermosetting resin used in the adhesive linkage of the back side, such as polyurethane resin, epoxy can be enumerated Resin etc..These thermosetting resins can be used alone, and two or more can also be applied in combination.
The manufacture method of cosmetic sheet
The cosmetic sheet of first invention for example can pass through following 1A processes and 2A processes manufacture.
1A processes：Formation has with concaveconvex shape, by the solidfied material of hardening resin composition in substrate layer superimposed layer The laminated body of the superficial layer of formation；
2A processes：The thermoplastic resin that can be peeled off is formed on the superficial layer of the laminated body obtained in above-mentioned 1A processes Adipose membrane layer.
In the first process and the second process of the first invention, composition used in each layer, the forming method of each layer are formed Actual conditions, the forming method of concaveconvex shape etc. of superficial layer 2 is as described above described in the project of the composition of each layer.
On the superficial layer 2 not in the case of other above-mentioned layers (bonding adhesive linkage 31, release layer 32 etc.) of lamination, 2A Process can for example be carried out by following process：
By extrusion molding or heat lamination, on superficial layer 2, the recess of the concaveconvex shape of superficial layer 2 is filled The process that mode forms the thermoplastic resin film layer that can be peeled off.
In addition, in the bonding adhesive linkage 31 that is formed by bonding agent of superimposed layer and thermoplastic resin film layer 30 of superficial layer 2 In the case of, 2A processes can for example be carried out by following process：
Coating forms the resin combination of bonding agent on superficial layer 2, by the recessed of the concaveconvex shape of above-mentioned superficial layer 2 The process that the mode of portion's landfill forms bonding adhesive linkage 31；With
In the process for the thermoplastic resin film layer 30 that the superimposed layer of above-mentioned bonding adhesive linkage 31 can be peeled off.
In addition, in the case of the superimposed layer release layer 32 of superficial layer 2 and thermoplastic resin film layer 30,2A processes are for example It can be carried out by following process：
Coating forms the resin combination of release layer 32 on superficial layer 2, by the concaveconvex shape of above-mentioned superficial layer 2 The process that the mode of recess landfill forms release layer 32；With
In the process for the thermoplastic resin film layer 30 that the superimposed layer of above-mentioned release layer 32 can be peeled off.
In addition, by the lamination bodily form of release layer 32, bonding adhesive linkage 31 and thermoplastic resin film layer 30 on superficial layer 2 In the case of, 2A processes can for example be carried out by following process：
Coating forms the resin combination of release layer 32 on superficial layer 2, by the concaveconvex shape of above-mentioned superficial layer 2 The process that the mode of recess landfill forms release layer 32；
Coating forms the resin combination of bonding agent on release layer 32, by the concaveconvex shape of above-mentioned superficial layer 2 The process that the mode of recess landfill forms bonding adhesive linkage 31；With
The process of multilayer thermoplastic resin film layer 30 on above-mentioned bonding adhesive linkage 31.
On the other hand, the cosmetic sheet of the second invention can for example pass through following 1B processes~3B processes manufacture.
1B processes：Prepare the superficial layer 2 with concaveconvex shape；
2B processes：On superficial layer 2, bonding is coated with a manner of the recess of the concaveconvex shape of superficial layer 2 to be filled Agent, lamination adhesive linkage 31；
3B processes：In the superimposed layer stripping film layer 33 of adhesive linkage 31.
In 1B processes~3B processes, formed composition used in each layer, each layer forming method actual conditions, Forming method of the concaveconvex shape of superficial layer 2 etc. is as described above described in the project of the composition of each layer.
Also, form the situation of concavo-convex protective layer 3 in the laminated body by release layer 32, adhesive linkage 31 and stripping film layer 33 Under, 2B processes and 3B processes can for example be carried out by following process：
Coating forms the resin combination of release layer 32 on superficial layer 2, by the recess of the concaveconvex shape of superficial layer 2 The process that the mode of landfill forms release layer 32；
The coating adhesive on release layer 32, formed in a manner of the recess of the concaveconvex shape of superficial layer 2 is filled viscous The process for connecing layer 31；With
In the process of the superimposed layer stripping film layer 33 of adhesive linkage 31.
In addition, in the case where forming superficial layer 2 by resin film, 1B processes can for example be carried out by following process：
Prepare the process of superficial layer 2 being made up of resin film；With
Processing is embossed on superficial layer 2, in the process that the surface of superficial layer 2 forms concaveconvex shape.
In these cases, when patterned layer 5, other layer of priming coat 4 etc. are formed between substrate layer 1 and superficial layer 2, pass through Following process is carried out：
The process of other layers such as lamination patterned layer 5, priming coat 4 on substrate layer 1；With
In the process for the superficial layer 2 that the superimposed layer of other layers such as patterned layer 5, priming coat 4 is made up of resin film；With
Processing is embossed on superficial layer 2, in the process that the surface of superficial layer 2 forms concaveconvex shape.
2. the decorated resin products formed with thermoplastic resin film layer
The decorated resin products formed with thermoplastic resin film layer of first invention and the second invention is by making into respectively The products formed that type resin is integrated with the cosmetic sheet of the first invention and the second invention and is molded.That is, the first invention carries thermoplastic The decorated resin products formed of property resin film layer is characterised by：At least lamination has forming resin layer 8, substrate layer 1, with recessed successively The superficial layer 2 and thermoplastic resin film layer 30 of convex form, superficial layer 2 are formed by the solidfied material of hardening resin composition.Fig. 7, 8 represent the cross section structure of a mode of the decorated resin products formed with thermoplastic resin film layer of the first invention.
In addition, the decorated resin products formed with concavo-convex protective layer of the second invention is characterised by：At least lamination successively There are forming resin layer 7, the superficial layer 2 with concaveconvex shape and the concavo-convex protective layer 3 that can peel off, concavo-convex protective layer 3 is from surface 2 side of layer are risen to be possessed the adhesive linkage 31 of the recess landfill of the concaveconvex shape of superficial layer 2 and peels off film layer 33 successively.Figure 15 tables Show the cross section structure of a mode of the decorated resin products formed with concavo-convex protective layer of the second invention.
The decorated resin products formed with thermoplastic resin film layer of (the first invention and the second invention) of the invention can lead to Cross the substrate layer side injection resin for being included in the cosmetic sheet of the present invention and form the method manufacture of the process of forming resin layer.Specifically For, using the cosmetic sheet of the present invention, by insert-molding method, injection moulding, decorative method, blow molding method, gas inject simultaneously The various injection mouldings such as the method for forming make.Thermoplastic is carried by the way that the cosmetic sheet of the present invention is made for various injection mouldings Property resin film layer decorated resin products formed, can play and suppress the above-mentioned effect that suffers damage of concaveconvex shape in injection moulding Fruit, therefore, as the preferred of the forming resin layer 8 for forming the decorated resin products formed with thermoplastic resin film layer of the invention One, can enumerate by be injection moulded formed injecting resin layer.In these injection mouldings, preferably enumerate inserts into Type method and injection moulding while decorative method.
During using insert-molding method, vacuum forming mould is utilized first in vacuum forming process by the cosmetic sheet of the present invention Advance vacuum forming (offline preforming) is surface of the molded article shape, cuts unnecessary part then according to needs, obtains into Matrix.The matrix band is inserted into injecting molding die, by injecting molding die matched moulds, to the resin of mold-in injection flow regime, Make its solidification, while injection moulding, make the side of substrate layer 1 of cosmetic sheet integrated with the outer surface of resin formed product, thus Decorated resin products formed of the manufacture with thermoplastic resin film layer.
More specifically, the present invention can be made by the insert-molding legal system including following processes carries thermoplasticity The decorated resin products formed of resin film layer：
Vacuum forming process using vacuum forming mould by the cosmetic sheet advance comprising of the present invention for three-dimensional shape；
The unnecessary part of cosmetic sheet obtained from cutting vacuum forming, obtains the process of matrix band；With
The matrix band obtained in above-mentioned operation is inserted into injecting molding die, injecting molding die is closed, to mold-in injection The resin of flow regime, by the resin process integrated with matrix band.
In vacuum forming process in insert-molding method, cosmetic sheet can be heated and be molded.
Heating-up temperature now is not particularly limited, can be according to the species of resin and the thickness of cosmetic sheet for forming cosmetic sheet The appropriate selection such as degree, such as in the case where using ABS resin film as substrate layer, typically 100~250 DEG C or so, Preferably 130~200 DEG C or so.In addition, in integrated process, the temperature of the resin of flow regime is not particularly limited, and leads to Often it is 180~320 DEG C or so, is preferably 220~280 DEG C or so.
In addition, when using injection moulding decorative method simultaneously, the cosmetic sheet of the present invention is configured provided with injection molding Suction hole is also used as on the former of vacuum forming mould, carries out preforming (online preforming) using the former, afterwards, will note Mould matched moulds is penetrated, the resin of flow regime is filled to mold-in injection, makes its solidification, while injection moulding, makes this hair The side of substrate layer 1 of bright cosmetic sheet is integrated with the outer surface of resin formed product, and thus manufacture carries thermoplastic resin film layer Decorated resin products formed.
More specifically, the band of the present invention of decorative method manufacture simultaneously of the injection moulding including following processes can be passed through There is the decorated resin products formed of thermoplastic resin film layer.
By the cosmetic sheet of the present invention with the base material of decorative sheet described above and the moveable die of the forming surface with regulation shape The mode of the forming surface opposite face is set, and cosmetic sheet heating is made into its softening afterwards, and carry out very from above-mentioned moveable die side Suction is drawn, and makes the cosmetic sheet after softening closely sealed along the forming surface of the moveable die, thus by the preforming process of cosmetic sheet；
After with the moveable die along the closely sealed cosmetic sheet of forming surface and fixing mould matched moulds, formed in two moulds Die cavity in injection fillers flow regime resin molding material, make its solidification, thus by the resin-formed body and decoration of formation The injection moulding process of piece laminated integratedization；With
Moveable die is set to leave fixing mould, the process for taking out the resin-formed body that lamination cosmetic sheet whole layer forms.
In the injection moulding simultaneously preforming operation of decorative method, the heating-up temperature of cosmetic sheet is not particularly limited, according to The appropriate selection such as the species of the resin of cosmetic sheet and the thickness of cosmetic sheet is formed, is using polyester resin film, acrylic acid tree In the case that adipose membrane is as substrate layer, typically 70~130 DEG C or so.In addition, in process is injection moulded, flow regime The temperature of resin be not particularly limited, typically 180~320 DEG C or so, be preferably 220~280 DEG C or so.
In addition, the decorated resin products formed of the present invention can also glue by vacuum compressing method etc., by the cosmetic sheet of the present invention The trailing being attached on pre-prepd three-dimensional resin-formed body (forming resin layer) makes.
When using vacuum compressing method, first, by the first vacuum chamber positioned at upside and the second vacuum positioned at downside In the vacuum compressing machine that room is formed, by the cosmetic sheet of the present invention and resin-formed body using cosmetic sheet as the first vacuum chamber side, resin Formed body is arranged on for the mode of the second vacuum chamber side and the mode on the side of substrate layer 1 towards the resin forming side of cosmetic sheet In vacuum compressing machine, two vacuum chambers are made to form vacuum state.What resin-formed body was arranged on that the second vacuum chamber side possesses can On the lifting platform of oscilaltion.Then, the first vacuum chamber is pressurizeed, and formed body is supported with cosmetic sheet using lifting platform Connect, using the pressure differential between two vacuum chambers, cosmetic sheet is pasted onto to the surface of resin-formed body in stretching.Finally, by two It is atmospheric pressure that individual vacuum chamber, which opens, cuts the unnecessary part of cosmetic sheet as needed, thus, it is possible to obtain the dress of the present invention Adorn synthetic resin.
In vacuum compressing method, before the process for abutting above-mentioned formed body with cosmetic sheet, in order that cosmetic sheet softens To improve mouldability, the process heated to cosmetic sheet is preferably provided with.The vacuum compressing method for possessing the process is sometimes special Ground is referred to as heating in vacuum crimping.Heating-up temperature in the process is according to the species of resin and the thickness of cosmetic sheet for forming cosmetic sheet The appropriate selection such as degree, in the case where using polyester resin film, acrylic resin film as substrate layer, usually 60~ 200 DEG C or so.
In the decorated resin products formed with thermoplastic resin film layer of the present invention, forming resin layer selection and purposes phase Corresponding moulding resin and formed.Can be thermoplastic resin, or thermosetting resin as moulding resin.
As the thermoplastic resin as moulding resin, for example, can enumerate the polyolefin-based resins such as polyethylene, polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride resin etc..These thermoplastic resins can be single 1 kind is solely used, two or more can also be applied in combination.
In addition, as the thermosetting resin as moulding resin, such as polyurethane resin, epoxy resin etc. can be enumerated. These thermosetting resins can be used alone, and two or more can also be applied in combination.
By the way that thermoplastic resin film layer is peeled off from the decorated resin products formed with thermoplastic resin film layer of the present invention Remove, decorated resin products formed can be obtained.In addition, in the decorated resin products formed with thermoplastic resin film layer, thermoplastic Property resin film layer play the effect for the screening glass for being used as decorated resin products formed, therefore can not peel off after fabrication and as former state Retain, when in use again peel off thermoplastic resin film layer.By using in this way, rubbing during because of transport can be prevented Wiping etc. causes to damage to decorated resin products formed.
3. decorated resin products formed
In the first invention, by from the above-mentioned decorated resin products formed with thermoplastic resin film layer by thermoplastic resin Film layer 30, which is peeled off, to be removed, and can obtain the decorated resin products formed that surface has been assigned concaveconvex shape.Also, in thermoplastic resin In the case that lamination has bonding adhesive linkage 31, other layers such as release layer 32 between film layer 30 and superficial layer 2, other layers also with heat Plastic resin film layer 30 is stripped removing simultaneously.From the above-mentioned decorated resin products formed with thermoplastic resin film layer by thermoplastic Property resin film layer 30 peel off remove when, superficial layer 2 just appears in the surface of decorated resin products formed, is in by its concaveconvex shape Reveal excellent design sense and hand sense of touch.Figure 10,11 represent from Fig. 7,8 decorated resin with thermoplastic resin film layer respectively Products formed eliminates the cross section structure of a mode of the decorated resin products formed after thermoplastic resin film layer 30.
In addition, in the second invention, by being protected from the above-mentioned decorated resin products formed with concavo-convex protective layer by bumps Layer 3, which is peeled off, to be removed, and can obtain the decorated resin products formed that surface has been assigned concaveconvex shape.Concavo-convex protective layer is carried from above-mentioned Decorated resin products formed by supporting mass peel off remove when, superficial layer 2 just appears in the surface of decorated resin products formed, passes through Its concaveconvex shape shows excellent design sense and hand sense of touch.Figure 16 is represented after concavo-convex protective layer 3 is eliminated in the second invention Decorated resin products formed a mode cross section structure.
The decorated resin products formed of first invention and the second invention have design sense excellent caused by concaveconvex shape and Hand sense of touch, it is thus possible to built-in material or exterior material as the vehicle such as automobile；The finishing materials such as washboard, linea angulata； The construction materials such as window frame, doorframe；The built-in material of the buildings such as wall, floor, ceiling；The household electrical appliances such as television receiver, air conditioner The basket of product；Container etc..
Embodiment
The present invention will be described in detail for embodiment exemplified below and comparative example.But the present invention is not limited to embodiment.
[manufacture of cosmetic sheet]
Embodiment 1A
As substrate layer, use ABS resin film (200 μm of thickness).On the substrate layer, using containing acrylic resin Ink composite, the patterned layer (5 μm of thickness) of wood grain style is formed by intaglio printing.In patterned layer, coating contains bonding The priming coat resin combination of agent resin, the adhesive resin is by containing host (acrylic polyol/polyurethane, mass ratio 9/1) the biliquid gel-type resin of 100 mass parts and the mass parts of curing agent (hexamethylene diisocyanate) 7 is formed, and makes above-mentioned bottom Coating resin compsn is dried, and forms the priming coat of 2 μm of thickness, obtaining lamination successively has substrate layer/patterned layer/priming coat Laminated body.
In the priming coat side of laminated body obtained above, processing is embossed, the recessed of sparrow pecked is formed on priming coat Convex form.The embossing plate deep (from concave bottom to the height of convex portion upper surface) of embossing plate used in embossing processing is 60 μm. Then, ionizing radiation curable resin combination (EB1) described later is coated with the priming coat formed with concaveconvex shape so that Gu Thickness after change reaches 8 μm.To resin combination irradiation accelerating potential 165kV, exposure dose 50kGy (5Mrad) electronics Ray makes its solidification, forms the superficial layer with concaveconvex shape.
Then, polyethylene layer is formed on superficial layer by extrusion molding, has substrate layer/figure so as to obtain lamination successively The cosmetic sheet of the laminated construction of pattern layer/priming coat/superficial layer/thermoplastic resin film layer (polyethylene film) with concaveconvex shape. Wherein, the condition as extrusion molding, temperature under the mould of extruder is set to 230~250 DEG C, the thickness of polyethylene layer is set to 50μm。
Embodiment 2A
It is same with embodiment 1A to operate, have in lamination successively and tool is formed on the laminated body of substrate layer/patterned layer/priming coat There is the superficial layer of concaveconvex shape.Then, the polyethylene film (μ of thickness 30 from the superimposed layer of superficial layer as thermoplastic resin film layer M), it is by lamination methods, superficial layer is Nian Jie with thermoplastic resin film layer, it is in addition, same with embodiment 1A to operate, obtain Lamination has the laminated construction of substrate layer/patterned layer/priming coat/superficial layer/thermoplastic resin film layer with concaveconvex shape successively Cosmetic sheet.Wherein, the condition as lamination methods, by heating-up temperature be set to 200~230 DEG C, pressure be set to 5kgf, polyethylene The thickness of film is set to 50 μm.
Embodiment 3A
As formed superficial layer ionizing radiation curable resin combination, replace EB1 using EB2 described later, except this with Outside, same with embodiment 1A to operate, obtaining lamination successively has substrate layer/patterned layer/priming coat/surface with concaveconvex shape The cosmetic sheet of the laminated construction of layer/thermoplastic resin film layer.
Embodiment 4A
As the ionizing radiation curable resin combination for forming superficial layer, EB1 is replaced using EB2, in addition, with reality Apply a 1A equally to operate, on the laminated body that lamination successively has substrate layer/patterned layer/priming coat, formation has concaveconvex shape Superficial layer.Then, ionizing radiation curable resin combination (EB3) described later is coated with superficial layer so that after solidification Thickness reach 10 μm.Make its solidification to resin combination irradiation accelerating potential 165kV, exposure dose 50kGy (5Mrad), Release layer is formed on superficial layer.Then, the bonding agent being made up of polyester and resin composition is coated with release layer so that Thickness after solidification reaches 30 μm, and bonding adhesive linkage is formed in a manner of the recess of the concaveconvex shape of superficial layer to be filled.Then, From multilayer thermoplastic resin film layer (30 μm of polyethylene film, thickness) on bonding adhesive linkage, obtaining lamination successively has substrate layer/figure The laminated construction of pattern layer/priming coat/superficial layer/release layer/bonding adhesive linkage/thermoplastic resin film layer with concaveconvex shape Cosmetic sheet.
Comparative example 1A
Acrylic resin film (75 μm of thickness) is used as superficial layer.On the superficial layer, using containing acrylic resin Ink composite, pass through intaglio printing formed wood grain style patterned layer (5 μm of thickness).In the patterned layer superimposed layer as base The ABS resin film (200 μm of thickness) of material layer.Then, in the surface of the photons of resulting laminated body, use and embodiment Embossing plate same 1A is embossed processing, and the concaveconvex shape of sparrow pecked is formed on superficial layer.Then, it is same with embodiment 1A Sample forms thermoplastic resin film layer (polyethylene layer) by extrusion molding on the superficial layer with concaveconvex shape, is folded successively Layer has the cosmetic sheet of the laminated construction of substrate layer/patterned layer/superficial layer/thermoplastic resin film layer with concaveconvex shape.
Embodiment 5A
As substrate layer, use ABS resin film (400 μm of thickness).On the substrate layer, using containing acrylic resin Ink composite, the patterned layer (5 μm of thickness) of wood grain style is formed by intaglio printing.In patterned layer, coating contains bonding The priming coat resin combination of agent resin, the adhesive resin is by containing host (acrylic polyol/polyurethane, mass ratio 9/1) the biliquid gel-type resin of 100 mass parts and the mass parts of curing agent (hexamethylene diisocyanate) 7 is formed, and makes above-mentioned bottom Coating resin compsn is dried, and forms the priming coat that thickness is 2 μm, obtaining lamination successively has substrate layer/patterned layer/priming coat Laminated body.Then, ionizing radiation curable resin combination (UV) described later is printed by silk-screen printing, forms diameter 2mm Point, and coating thickness is reached 30 μm.Accumulative light quantity 600mJ/cm is irradiated to the uncured resin layer2Ultraviolet, make ionization Radiation-hardenable resins solidify, and form the superficial layer with concaveconvex shape.Then, formed by extrusion molding on superficial layer Polyethylene layer, there is substrate layer/patterned layer/priming coat/superficial layer/thermoplastic resin with concaveconvex shape so as to obtain lamination successively The cosmetic sheet of the laminated construction of adipose membrane layer (polyethylene film).Wherein, the condition as extrusion molding, by temperature under the mould of extruder Be set to 230~250 DEG C, the thickness of polyethylene layer be set to 50 μm.
Embodiment 6A
Same with embodiment 5A to operate, obtaining lamination successively has the laminated body of substrate layer/patterned layer/priming coat.Then, lead to Cross rod painting and ionizing radiation curable resin combination (EB3) described later is coated with priming coat so that the thickness after solidification reaches To 10 μm.To uncured resin layer irradiation accelerating potential 165kV, exposure dose 50kGy (5Mrad) electron ray, set Resin bed.Then, it is same with embodiment 5A to operate on resin bed, form superficial layer, thermoplastic resin with concaveconvex shape Adipose membrane layer, obtaining lamination successively has substrate layer/patterned layer/priming coat/resin bed/superficial layer/thermoplasticity with concaveconvex shape The cosmetic sheet of the laminated construction of resin film layer (polyethylene film).
Embodiment 7A
It will be made using the polymethyl methacrylate acrylic resin piece transparent as the non-coloring of 75 μm of the thickness of main component For resin bed, it is bonded at the back side of resin bed successively lamination by polymethyl methacrylate and biliquid curable polyurethane resin system The bond layer (10 μm of thickness) of agent composition, the patterned layer (5 μm of thickness) of wood grain style, afterwards, by dry lamination, from pattern The substrate layer (400 μm of thickness) that the superimposed layer of layer is made up of ABS resin, obtaining lamination successively has substrate layer/patterned layer/bonding agent The laminated body of layer/resin bed.Then, it is same with embodiment 5A to operate, form superficial layer, thermoplastic resin with concaveconvex shape Film layer, obtaining lamination successively has substrate layer/patterned layer/bond layer/resin bed/superficial layer/thermoplasticity with concaveconvex shape The cosmetic sheet of the laminated construction of resin film layer (polyethylene film).
Embodiment 8A
Same with embodiment 5A to operate, obtaining lamination successively has substrate layer/patterned layer/priming coat/have concaveconvex shape The laminated body of superficial layer.Then, on superficial layer, by extrusion molding lamination A-PET films, thus obtaining lamination successively has The laminated construction of substrate layer/patterned layer/priming coat/superficial layer/thermoplastic resin film layer (A-PET) with concaveconvex shape Cosmetic sheet.Wherein, the condition as extrusion molding, by temperature under the mould of extruder is set to 250~260 DEG C, the thickness of pet layer sets For 50 μm.
Comparative example 2A
It is same with embodiment 5A to operate in addition to not forming thermoplastic resin film layer, obtain lamination successively have substrate layer/ The cosmetic sheet of the laminated construction of patterned layer/priming coat/superficial layer with concaveconvex shape.
Comparative example 3A
In addition to not forming thermoplastic resin film layer, in the same manner as embodiment 6A obtaining lamination successively has substrate layer/figure The cosmetic sheet of the laminated construction of pattern layer/priming coat/resin bed/superficial layer with concaveconvex shape.
Comparative example 4A
It is same with embodiment 7A to operate in addition to not forming thermoplastic resin film layer, obtain lamination successively have substrate layer/ The cosmetic sheet of the laminated construction of patterned layer/bond layer/resin bed/superficial layer with concaveconvex shape.
[manufacture of decorated resin products formed]
Each cosmetic sheet is heated to 160 DEG C using infrared heater, makes its softening.Then, using vacuum forming mould Tool carries out vacuum forming (maximum tension multiplying power 100%), and preforming and matched moulds is carried out in a manner of the interior shape along mould. Afterwards, to the mould intracavitary administration makrolon of mould and ABS hybrid resin, integration is carried out to the cosmetic sheet and moulding resin Shaping, obtain the decorated resin products formed with thermoplastic resin film layer.Then, thermoplastic resin film is carried from what is obtained with hand The decorated resin products formed of layer peels off thermoplastic resin film layer, so as to obtain decorated resin products formed.Wherein, in embodiment 1A In~8A and comparative example 1A cosmetic sheet, the layer of concaveconvex shape of superficial layer will be protected as thermoplastic resin film layer, thus three It is excellent to tie up mouldability.
The evaluation ＞ of the concaveconvex shape of ＜ cosmetic sheets
In the manufacturing process of embodiment and the cosmetic sheet of comparative example, for the surface before and after formation thermoplastic resin film layer The change of the concaveconvex shape of layer, is evaluated concave-convex sense by vision and hand sense of touch.Wherein, thermoplastic resin film layer is from decoration The stripping of piece, thermoplastic resin film layer is peeled off from cosmetic sheet by using hand and carried out.Metewand is as described below.Result is shown In table 1A, 2A.
〇：Concave-convex sense has almost no change.
△：Concave-convex sense changes, and even in being peeled off after forming thermoplastic resin film layer, can also feel concavo-convex Sense.
×：Concave-convex sense, which has, significantly to be changed, after thermoplastic resin film layer is peeled off, imperceptible concave-convex sense.
The evaluation ＞ of the concaveconvex shape of ＜ decorated resin products formeds
On the change by the concaveconvex shape before and after each cosmetic sheet manufacture decorated resin products formed, pass through vision and hand sense of touch Concave-convex sense is evaluated.Metewand is as described below.Show the result in table 1A, 2A.
〇：After decorated resin products formed is made, concave-convex sense also has almost no change, and is strongly felt bumps Sense.
△：After decorated resin products formed is made, concave-convex sense changes, but decorated resin products formed can also be felt Concave-convex sense.
×：After decorated resin products formed is made, concave-convex sense, which has, significantly to be changed, and decorated resin products formed is felt not To concave-convex sense.
[table 1A]
[table 2A]
EB1
2 function polycarbonate acrylic ester (weight average molecular weight：10,000)：95 mass parts
4 functional polyurethanes acrylate oligomer (weight average molecular weight：6,000)：5 mass parts
EB2
2 function polycarbonate acrylic ester (weight average molecular weight：8,000)：95 mass parts
2 function Silicone acrylates oligomer (weight average molecular weight：6,000)：5 mass parts
EB3
3 function pentaerythritol acrylate (weight average molecular weight：300)：30 mass parts
Acrylate copolymer (weight average molecular weight 120,000)：70 mass parts
UV
Polyurethane series acrylate oligomer (weight average molecular weight about 8000)：20 mass parts
2 functional acrylate's monomers：60 mass parts
Photosensitive compounds：5 mass parts
Photoepolymerizationinitiater initiater：5 mass parts
Filler and pigment：10 mass parts
Bond the polyester and resin composition of adhesive linkage
The ﹕ 10 of Ju Zhi Duo Yuan Chun ﹕ isocyanates=100
Polyethylene after extrusion molding
Extrude grade low density PE
Polyethylene film after heat lamination
Low density PE film
In embodiment 7A, on the resin bed that the acrylic resin film (thermoplastic resin) by partly exposing is formed, directly Connect thermoplastic resin film extruding forming, but the evaluation of the concaveconvex shape of decorated resin products formed is excellent.Can be with according to the result Think：The shape for the superficial layer (protuberance layer) that the concave-convex sense of decorated resin products formed is made up of curable resin dominates, and is squeezing When going out to be molded, even if acrylic resin film, there occurs a little deformation, as long as superficial layer does not deform, concave-convex sense would not become Difference.
Embodiment 9A
On superficial layer, polyethylene is replaced to carry out extrusion molding using A-PET, it is in addition, same with embodiment 1A Operation, obtaining lamination successively has substrate layer/patterned layer/priming coat/superficial layer/thermoplastic resin film layer with concaveconvex shape The cosmetic sheet of the laminated construction of (A-PET films).Using resulting cosmetic sheet decorated resin is manufactured in the same manner as other embodiment During products formed, three-dimensionally shaped property is good, and cosmetic sheet and decorated resin products formed have arrived concave-convex sense in surface feel.In addition, In portion slightly there occurs cast gate flowing in embodiment 1A, but unconfirmed in embodiment 9A arrive the phenomenon.In addition, in reality Apply in a 1A, the suction hole of the former after shaping sees the residue of thermoplastic resin film, but unconfirmed arrive should in embodiment 9A Phenomenon.
Embodiment 10A
As the ionizing radiation curable resin combination for forming superficial layer, EB1 is replaced (wherein, after with solidification using EB2 Thickness reach 30 μm of mode and be coated), in addition, same with embodiment 1A to operate, obtaining lamination successively has base material The cosmetic sheet of the laminated construction of layer/patterned layer/priming coat/superficial layer/thermoplastic resin film layer with concaveconvex shape.With implementation Example 1A~8A is equally operated, and carries out the evaluation of the concaveconvex shape of cosmetic sheet and decorated resin products formed.Show the result in table 3A.Its In, in embodiment 1A~8A, by the vacuum forming of the cosmetic sheet during evaluation, superficial layer is not cracked etc. yet, but In embodiment 10A, because the thickness of superficial layer is somewhat thick, reach 30 μm, thus occur slightly by being molded over superficial layer Crackle.
Embodiment 11A
As the ionizing radiation curable resin combination for forming superficial layer, EB1 is replaced (wherein, after with solidification using EB2 Thickness reach 50 μm of mode and be coated), in addition, same with embodiment 1A to operate, obtaining lamination successively has base material The cosmetic sheet of the laminated construction of layer/patterned layer/priming coat/superficial layer/thermoplastic resin film layer with concaveconvex shape.With implementation Example 1A~8A is equally operated, and carries out the evaluation of the concaveconvex shape of cosmetic sheet and decorated resin products formed.Show the result in table 3A.Its In, in embodiment 1A~8A, even if also not cracked by the vacuum forming of the cosmetic sheet during evaluation, superficial layer Deng, but in embodiment 11A, there is crackle because the thickness of superficial layer is thick, thus by being molded over superficial layer.
[table 3A]
[manufacture of cosmetic sheet]
Embodiment 1B
As substrate layer, use ABS resin film (200 μm of thickness).On the substrate layer, using containing acrylic resin Ink composite, the patterned layer (5 μm of thickness) of wood grain style is formed by intaglio printing.In patterned layer, coating contains bonding The priming coat resin combination of agent resin, the adhesive resin is by containing host (acrylic polyol/polyurethane, mass ratio 9/1) 100 parts are formed with the biliquid gel-type resin of 7 parts of curing agent (hexamethylene diisocyanate), make above-mentioned priming coat tree Oil/fat composition is dried, and forms the priming coat of 2 μm of thickness, obtaining lamination successively has the laminated body of substrate layer/patterned layer/priming coat.
In the priming coat side of laminated body obtained above, processing is embossed, the recessed of sparrow pecked is formed on priming coat Convex form.The embossing plate deep (from concave bottom to the height of convex portion upper surface) of embossing plate used in embossing processing is 60 μm. Then, on the priming coat formed with concaveconvex shape, it is coated with ionizing radiation curable resin combination (EB1) described later so that Thickness after solidification reaches 8 μm.To resin combination irradiation accelerating potential 165kV, exposure dose 50kGy (5Mrad) electricity Sub- ray, make its solidification, form the superficial layer with concaveconvex shape.
Then, the bonding agent being made up of polyester and resin composition is coated with superficial layer so that the thickness after solidification reaches To 30 μm, adhesive linkage is formed in a manner of the recess of the concaveconvex shape of superficial layer to be filled.Then, from the superimposed layer of adhesive linkage by The stripping film layer (30 μm of thickness) that polyethylene is formed, obtaining lamination successively has substrate layer/patterned layer/priming coat/have concave-convex The cosmetic sheet of the laminated construction of the superficial layer of shape/concavo-convex protective layer (adhesive linkage/stripping film layer).
Embodiment 2B
As superficial layer, use acrylic resin film (75 μm of thickness).On the superficial layer, using containing acrylic resin Ink composite, pass through intaglio printing formed wood grain style patterned layer (5 μm of thickness).In patterned layer, lamination is as base The ABS resin film (200 μm of thickness) of material layer.Then, processing is embossed in the photons of resulting laminated body, on surface The concaveconvex shape of sparrow pecked is formed on layer.Embossing plate used in embossing processing is identical with embodiment 1B.Operated more than, Obtaining lamination successively has the laminated body of substrate layer/patterned layer/superficial layer with concaveconvex shape.Then, it is same with embodiment 1B Operation, in superimposed layer adhesive linkage, the stripping film of superficial layer, obtaining lamination successively has substrate layer/patterned layer/have concaveconvex shape The cosmetic sheet of the laminated construction of superficial layer/concavo-convex protective layer (adhesive linkage/stripping film layer).
Embodiment 3B
It is same with embodiment 1B to operate, after obtaining the laminated body that lamination successively has substrate layer/patterned layer/priming coat, make With ionizing radiation curable resin combination (EB2) described later, the superficial layer with concaveconvex shape is formed.On the other hand, upper State and ionizing radiation curable resin combination (EB3) described later is coated with superficial layer so that the thickness after solidification reaches 10 μm. To resin combination irradiation accelerating potential 165kV, exposure dose 50kGy (5Mrad), make its solidification, the shape on superficial layer Into release layer.
Then, the bonding agent being made up of polyester and resin composition is coated with release layer so that the thickness after solidification reaches To 30 μm, adhesive linkage is formed in a manner of the recess of the concaveconvex shape of superficial layer to be filled.Then, will be above-mentioned on adhesive linkage Film layer is peeled off from adhesive linkage side lamination, obtaining lamination successively has substrate layer/patterned layer/priming coat/surface with concaveconvex shape The cosmetic sheet of the laminated construction of layer/concavo-convex protective layer (release layer/adhesive linkage/stripping film layer).
Comparative example 1B
On the superficial layer with concaveconvex shape, polyethylene layer is formed by extrusion molding, in addition, with embodiment 2B is equally operated, and obtaining lamination successively has substrate layer/patterned layer/superficial layer/concavo-convex protective layer (polyethylene with concaveconvex shape Layer) laminated construction cosmetic sheet.Wherein, the condition as extrusion molding, temperature under the mould of extruder is set to 230~250 DEG C, the thickness of polyethylene layer is set to 50 μm.
Comparative example 2B
In the superimposed layer polyethylene film (50 μm of thickness) of the superficial layer with concaveconvex shape, by lamination methods by superficial layer Nian Jie with peeling off film layer, in addition, same with embodiment 1B to operate, obtaining lamination successively has substrate layer/patterned layer/primary coat The cosmetic sheet of the laminated construction of layer/superficial layer/concavo-convex protective layer (polyethylene film layer) with concaveconvex shape.Wherein, as heat The condition of laminating, heating-up temperature is set to 200~230 DEG C, pressure is set to 5kgf/cm2。
[manufacture of decorated resin products formed]
Each cosmetic sheet is heated into 160 DEG C using infrared heater makes its softening.Then, using vacuum forming mould Vacuum forming (maximum tension multiplying power 100%) is carried out, preforming and matched moulds is carried out in a manner of the interior shape along mould.It Afterwards, makrolon and ABS hybrid resin are expelled in the die cavity of mould, integration is carried out to the cosmetic sheet and moulding resin Shaping, obtain the decorated resin products formed with concavo-convex protective layer.Then, with hand from the resulting dress with concavo-convex protective layer Decorations synthetic resin peels off concavo-convex protective layer, so as to obtain decorated resin products formed.
The evaluation ＞ of ＜ concaveconvex shapes
In order to evaluate the concaveconvex shape on the surface of decorated resin products formed, surface roughness, contour shape measuring machine are used (Tokyo Seimitsu Co., Ltd Handysurf E-35A), measure center line average roughness (Ra), maximum height (Rmax) With 10 average heights (Rz).Show the result in table 1B.
The evaluation ＞ of the concaveconvex shape of ＜ cosmetic sheets
In the manufacturing process of embodiment and the cosmetic sheet of comparative example, for the superficial layer before and after the concavo-convex protective layer of formation The change of concaveconvex shape, concave-convex sense is evaluated by vision and hand sense of touch.Wherein, stripping of the concavo-convex protective layer from cosmetic sheet Concavo-convex protective layer is peeled off from cosmetic sheet by using hand and carried out.Metewand is as described below.Show the result in table 1B.
〇：Concave-convex sense has almost no change.
△：Concave-convex sense varies slightly.
×：Concave-convex sense, which has, significantly to be changed, imperceptible concave-convex sense.
The evaluation ＞ of the concaveconvex shape of ＜ decorated resin products formeds
For the change by the concaveconvex shape before and after each cosmetic sheet manufacture decorated resin products formed, pass through vision and hand sense of touch Concave-convex sense is evaluated.Metewand is as described below.Show the result in table 1B.
〇：After decorated resin products formed is made, concave-convex sense also has almost no change, and is strongly felt bumps Sense.
△：After decorated resin products formed is made, concave-convex sense varies slightly.
×：After decorated resin products formed is made, concave-convex sense, which has, significantly to be changed, imperceptible concave-convex sense.
[table 1B]
In table 1B, "-" represents not to be measured.
EB1
2 function polycarbonate acrylic ester (weight average molecular weight：10,000)：95 mass parts
4 functional polyurethanes acrylate oligomer (weight average molecular weight：6,000)：5 mass parts
EB2
2 function polycarbonate acrylic ester (weight average molecular weight：8,000)：95 mass parts
2 function Silicone acrylates oligomer (weight average molecular weight：6,000)：5 mass parts
EB3
3 function pentaerythritol acrylate (weight average molecular weight：300)：30 mass parts
Acrylate copolymer (weight average molecular weight 120,000)：70 mass parts
The polyester and resin composition of adhesive linkage
The ﹕ 10 of Ju Zhi Duo Yuan Chun ﹕ isocyanates=100
Polyethylene in comparative example 1B after extrusion molding
Extrude grade low density PE
Polyethylene film in comparative example 2B after heat lamination
Low density PE film
Symbol description
1 substrate layer
2 superficial layers
3 concavo-convex protective layers
4 priming coats
5 patterned layers
6 transparent resin layers
7 resin beds
8 forming resin layers
30 thermoplastic resin film layers
31 bonding adhesive linkages
32 release layers
33 peel off film layer
34 adhesive linkages

Claims (17)

  1. A kind of 1. cosmetic sheet, it is characterised in that：
    At least lamination has substrate layer, formed by the solidfied material of hardening resin composition and has the surface of concaveconvex shape successively Layer and the thermoplastic resin film layer that can be peeled off.
  2. 2. cosmetic sheet as claimed in claim 1, it is characterised in that：
    The superficial layer is formed by the solidfied material of ionizing radiation curable resin combination.
  3. 3. cosmetic sheet as claimed in claim 1 or 2, it is characterised in that：
    The thermoplastic resin film layer contains non-crystalline polyester resin.
  4. 4. such as cosmetic sheet according to any one of claims 1 to 3, it is characterised in that：
    The thermoplastic resin film layer is stacked in by extrusion molding or heat lamination on the concaveconvex shape of the superficial layer.
  5. 5. such as cosmetic sheet according to any one of claims 1 to 4, it is characterised in that：
    The thermoplastic resin film layer fills the recess of the concaveconvex shape of the superficial layer.
  6. 6. such as cosmetic sheet according to any one of claims 1 to 5, it is characterised in that：
    Lamination has bonding adhesive linkage between the superficial layer and the thermoplastic resin film layer.
  7. 7. such as cosmetic sheet according to any one of claims 1 to 6, it is characterised in that：
    There is priming coat in the lower stacks close to the superficial layer.
  8. 8. such as cosmetic sheet according to any one of claims 1 to 7, it is characterised in that：
    Lamination has patterned layer between the substrate layer and the superficial layer.
  9. 9. such as cosmetic sheet according to any one of claims 1 to 8, it is characterised in that：
    The concaveconvex shape of the superficial layer is exposed under the superficial layer by the convex portion that partly sets and between the convex portion The recess of layer is formed.
  10. 10. such as cosmetic sheet according to any one of claims 1 to 9, it is characterised in that：
    The thickness of the superficial layer is 0.01~30 μm.
  11. A kind of 11. manufacture method of cosmetic sheet, it is characterised in that including：
    The first process of laminated body is formed, the laminated body has with concaveconvex shape and by curable resin group in substrate layer superimposed layer The superficial layer that the solidfied material of compound is formed；With
    On the superficial layer of the laminated body obtained in first process, thermoplastic resin film layer that lamination can be peeled off Second process.
  12. 12. the manufacture method of cosmetic sheet as claimed in claim 11, it is characterised in that：
    The thermoplastic resin film layer contains non-crystalline polyester resin.
  13. 13. the manufacture method of the cosmetic sheet as described in claim 11 or 12, it is characterised in that：
    Second process includes following process：
    On superficial layer, by extrusion molding or heat lamination, the side that the recess of the concaveconvex shape of the superficial layer is filled The process for the thermoplastic resin film layer that formula lamination can be peeled off.
  14. 14. the manufacture method of the cosmetic sheet as described in claim 11 or 12, it is characterised in that：
    Second process includes following process：
    The coating resin composition on superficial layer, lamination glues in a manner of the recess of the concaveconvex shape of the superficial layer to be filled The process for closing adhesive linkage；With
    The process that the thermoplastic resin film layer that can be peeled off is formed on the bonding adhesive linkage.
  15. A kind of 15. decorated resin products formed with thermoplastic resin film layer, it is characterised in that：
    At least lamination has forming resin layer, substrate layer, formed by the solidfied material of hardening resin composition and with bumps successively The superficial layer of shape and the thermoplastic resin film layer that can be peeled off.
  16. A kind of 16. manufacture method of the decorated resin products formed with thermoplastic resin film layer, it is characterised in that：
    It is included in the substrate layer side of cosmetic sheet according to any one of claims 1 to 10 by injecting resin and laminated forming tree The process of lipid layer.
  17. A kind of 17. manufacture method of decorated resin products formed, it is characterised in that：
    Including peeling off the thermoplastic resin from the decorated resin products formed with thermoplastic resin film layer described in claim 15 The process of adipose membrane layer.
CN201680018573.4A 2015-03-30 2016-03-30 Cosmetic sheet Pending CN107405891A (en)

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US20180043653A1 (en) 2018-02-15
EP3278982A1 (en) 2018-02-07
EP3278982A4 (en) 2018-11-14
CN113147109A (en) 2021-07-23
JP6965743B2 (en) 2021-11-10
KR102430212B1 (en) 2022-08-05
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WO2016159119A1 (en) 2016-10-06
JP2021176697A (en) 2021-11-11

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Application publication date: 20171128